Former Post Office boss Paula Vennells is handing back her CBE with immediate effect after facing mounting pressure over the Horizon IT scandal.
More than 700 sub-postmasters were prosecuted based on data from faulty Horizon software between 1999 and 2015.
Some people went to prison for false accounting and theft, while many were financially ruined.
More than a million people signed a petition calling for Ms Vennells to be stripped of her CBE.
Government ministers have promised a plan as soon as later this week to help hundreds of sub-postmasters clear their names.
One idea being explored is passing a new law that would exonerate hundreds wrongfully convicted.
In a statement, Ms Vennells, who was Post Office chief executive between 2012 and 2019, said she had "listened" to the sub-postmasters and others calling for her to return her CBE.
"I am truly sorry for the devastation caused to the sub-postmasters and their families, whose lives were torn apart by being wrongly accused and wrongly prosecuted as a result of the Horizon system."
Ms Vennells has long faced questions over her role in the scandal, which has been described as one of the most widespread miscarriages of justice the UK has seen.
While the scandal has been public knowledge for some time with a public inquiry ongoing, an ITV drama - Mr Bates vs The Post Office - which aired last week thrust the issue back into the spotlight.
A public inquiry into the scandal has been under way since February 2021, and will resume on Thursday following a break over Christmas.
Fujitsu - the Japanese technology company that manufactured the Horizon system - has been invited to answer questions from MPs next week.
The Business and Trade Select Committee says Post Office minister Kevin Hollinrake has confirmed he will attend the evidence session on 16 January.
Ms Vennells was appointed as CBE for services to the Post Office and to charity in the 2019 New Year's Honours - despite ongoing legal action against Post Office, which was launched by 555 sub-postmasters in 2017.
During her tenure, the Post Office repeatedly denied there were problems with the Horizon system.
The Post Office said the honour was given for her work on "diversity and inclusion", and her "commitment to the social purpose at the heart of the business and her dedication in putting the customer first".
However, despite the offer by Ms Vennells, the only person who can strip someone of an honour is King Charles.
People can indicate they would like to renounce their honour, as Ms Vennells has now done - but doing so has no formal effect. Until the King is advised by the Forfeiture Committee and acts on its advice, Ms Vennells will continue to hold her CBE.
The Communication Workers Union (CWU), which represents 110,000 employees of Royal Mail (which Post Office used to be part of)said Ms Vennells' decision was "a token gesture".
CWU's national officer Andy Furey also called for her to return performance-related bonuses she received during her role at Post Office.
He said: "Since she received these bonuses while overseeing the most widespread miscarriage of justice in British history, it would only be right to return this money."
Many victims of the scandal are still fighting to have their convictions overturned or to secure full compensation after being forced to pay out thousands of pounds of their own money for shortfalls that were caused by Horizon accounting software.
Jo Hamilton, a former subpostmistress who was wrongly convicted in 2008 of stealing thousands of pounds from a village shop in Hampshire, said she was glad Ms Vennells had agreed to return the honour.
"It's a shame it took just a million people to cripple her conscience," she said.
Downing Street has said it is "obviously the right decision" for Ms Vennells to return her CBE.
Former sub-postmaster Michael Rudkin, whose wife Susan was wrongly accused of stealing £44,000, said he was pleased that Ms Vennells had chosen to return her CBE.
He said he had written personally to Ms Vennells after his wife's prosecution to ask for a further investigation into her case, and received no help.
Mr Rudkin, who lost his job and union position due to the Horizon scandal, said his family had also lost friends due to the allegations.
A CBE (Commander of the British Empire) is awarded to someone who has gone "above and beyond for the community or country".
After a damehood or knighthood, it is the highest level of Order of the British Empire, and is followed by the OBE (Officer of the Order of the British Empire), then the MBE (Member of the Order of the British Empire).
Number 10 also said it would support "further recognition" of the work of sub-postmaster Alan Bates and others to expose the Horizon scandal.
Until 2012, the Post Office was part of Royal Mail before they were split into two. Between 2003 and 2010, the chief executive of Royal Mail was Adam Crozier who went on to lead ITV and is now chairman of BT.
He was replaced by Dame Moya Greene who ran Royal Mail for eight years, during which time the company was privatised and listed on the London Stock Exchange in 2013.
The government has been considering options to speed up justice for wrongfully convicted sub-postmasters.
On Tuesday, Justice Secretary Alex Chalk said the idea of using legislation to quash convictions of all Post Office workers caught up in the scandalwas under "active consideration".
Former minister Nadhim Zahawi has called for a "simple bill" to quash all the remaining convictions based on "bad data".
However, others have disagreed, including former attorney general Dominic Grieve who told the BBC that it would amount to "parliamentary interference in the judicial process".
Instead, he said each case "ought to be considered on its own merits", and sent to the Criminal Cases Review Commission (CCRC), which investigates alleged miscarriages of justice.
The scandal has been described as the most widespread miscarriage of justice in British history, but to date only 93 convictions have been overturned and of them, just 30 people have agreed "full and final" compensation settlements, meaning many victims are still fighting to clear their names.
Some 54 cases have resulted in either a conviction being upheld, people being refused permission to appeal, or the person appealing having withdrawn from the process.
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