Ten fire engines and around 70 firefighters were called to a fire at a derelict building on Coventry Close in Kilburn.
Part of the ground floor of the three-storey building was damaged by fire. Four people on the ground floor were helped to safety by firefighters at the rear of the building. One person was rescued from the first floor by firefighters via a short-extension ladder. Three people were rescued from the roof using one of the Brigade's 32-metre turntable ladders. Two people were taken to hospital by London Ambulance Service crews.
Station Commander Kevin Morgan, who was in attendance, said: "Due to heavy smoke, local residents were advised to keep their windows and doors shut.
"Motorists were advised to avoid the area due to a road closure on Kilburn High Road between Belsize Road and Oxford Road."
The Brigade's Control Officers received around 15 calls about the fire.
The Brigade was called at 1443 and Control Officers mobilised crews from West Hempstead, North Kensington, Paddington, Chelsea, Willesden and surrounding fire stations to the scene. The fire was under control by 1603.
The cause of the fire is under investigation by the Brigade and Metropolitan Police.