Cressida Dick was in charge when Mr de Menezes was shot
Ken Livingstone has said the police officer in charge when Jean Charles de Menezes was shot has the "potential" to be a future Met Police Commissioner.
A jury returned an open verdict at the inquest into the electrician's death.
The former Mayor of London said Cressida Dick was one of the "most talented" officers he had worked with.
But Gareth Pierce, a lawyer for the de Menezes family, said 25 "serious and catastrophic" failures by Ms Dick alone had been identified.
Brazilian Mr de Menezes, 27, was shot dead on 22 July 2005 at Stockwell Tube station when he was mistaken for a suicide bomber.
In an interview with BBC Radio 4's Today programme, Mr Livingstone said the police officers made mistakes because of the "unbelievable" pressure they were under.
Ms Dick, who was in command of the operation and subsequently promoted, had "commissioner potential" he said.
There were four men on the loose who tried to do suicide bombing. We knew we had a few days at most to catch them before they did it again and got it right
"Cressida Dick is one of the most talented officers I have ever worked with," he said, adding that she had an "incredible record".
"The truth is we don't really know much more today than 48 hours after the event - a tragic series of errors. Nobody thought there was a malignant mastermind behind it all," he said.
Although he accepted the police deserved criticism, he argued officers were not always in a position to interrogate a suspect they believed to be a potential terrorist.
"I was close to that operation. The pressures people were operating under were unbelievable.
"There were four men on the loose who tried to do suicide bombing. We knew we had a few days at most to catch them before they did it again and got it right. And under those pressures mistakes will happen."
Mr de Menezes - who was shot seven times by two officers at Stockwell - was, in fact, the 53rd victim of the London bombings of 7 July, he added.
But Gareth Pierce, one of the lawyers representing the family of Mr de Menezes, said too much attention had been put on the armed officers who shot Mr de Menezes.
A better focus, she said, would be on those in command.
"The handling of the events that led up to the fatal shooting was disastrous. It was disastrous on the part of the senior officers who had a public duty and were paid to exercise that duty of care."
The inquest had also revealed police officers had been trained to operate in what was "effectively a war situation", she said.
But, she continued, they did not know the basic terminology to use and appeared unable to set up an effective central command system with which to properly manage information.
"Jean Charles was tracked and eventually killed on the basis of a litany of assessments that ranged from 'Not him', 'Possibly him', 'Probably him' to the end - which propelled the armed officers - to 'That's him'."
The "extraordinary restrictions" placed on the jury - which was instructed not to return a verdict of unlawful killing - meant the police would not be properly "held to account" over the death and lessons would not be learned for the future, she added.
During the inquest, the 10 jury members were asked 12 specific questions about whether or not a series of events on 22 July 2005 contributed to Mr de Menezes' death.
Mr de Menezes was shot dead on a Tube train at Stockwell
Coroner Sir Michael Wright, who presided over the three-month inquest held at the Oval cricket ground in London, had previously said the facts did not justify allowing the jury to consider an unlawful killing.
Having been instructed not to return such a verdict, the jury went on to reject the police account he had been killed lawfully and returned an open verdict.
After the verdict was announced, the Menezes family lawyer said officers should be investigated for perjury - a call immediately rejected by the Independent Police Complaints Commission (IPCC).
Throughout the inquest, Metropolitan Police officers told the hearings they believed the Brazilian was one of the four failed bombers who attempted to strike London on 21 July 2005.
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