Scotland Yard's "shoot to kill" strategy has been widened from suicide bombers to offences such as kidnapping, stalking and domestic violence.
However, the decision to shoot a suspect in the head without the marksman giving a warning would only be used under exceptional circumstances, one of the country's most senior police chiefs said.
An Operation Kratos review has said officers could shoot to kill without issuing any challenge when an offender holding a weapon was thought to be on the brink of murder.
The use of a "shoot to kill" strategy against terrorists came under attack after police shot Brazilian Jean Charles de Menezes seven times in the head on July 22, after mistaking him for a suicide bomber.
There has been growing criticism of the lack of accountability surrounding the use of the tactic.
Met Police Assistant Commissioner said: "There are certain other circumstances [Kratos] could be applicable.
"For example, if there was a kidnap at gunpoint where the kidnapper was pointing the weapon at [the victim's] head and shouting they were about to shoot.
Alternatively it might be a stalking case where the victim had a gun pointed at their head and there was no clear shot to the stalker's body."
He stressed that under the existing law officers are already protected if they are found to have used "reasonable force".
House's review of Kratos states "there is no legal requirement for an officer to give a verbal challenge before firing" and the police's use of firearms manual "acknowledges that there are occasions when it is not appropriate or practical".
Figures in the review strategy indicate the Met Police has had more than 1000 reports from the public about suspected suicide bombers since July 21.
In response the police have sent out armed teams six times and alerted the Kratos response teams at least 11 times. The force has 12 specialist firearms units trained to deal with suspected bombers and other gunmen.
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'Shoot-to-kill' policy extended to cover other crimes
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