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The Police Watchdog says officers fired five shots at a 25 year old man in Forest Hill, hitting him three times.
Officers were called to Elsinore Road just after 5.40 am on Sunday after reports of a man armed with a knife attempting to steal a car.
The man's condition is stable in King's College Hospital after receiving injuries to his abdomen, leg and hand injuries.
The IPCC is now appealing for witnesses.
IPCC Commissioner Mike Franklin said: "On Monday afternoon myself and our independent investigators met with the man’s family and informed them of the IPCC's involvement and how our investigation will proceed.
"We are determined to thoroughly scrutinise the circumstances surrounding this shooting and the community can assist by coming forward with any information they may have regarding this incident.
"A young man remains in hospital but with help from eyewitnesses we can piece together bit-by-bit as much information as possible to form a clear sequence of events.
"I would urge anyone who can provide information to contact the IPCC by email at http://firstname.lastname@example.org or on freephone 0800 096 9077."