Eight fire engines and around 60 firefighters were called to a fire at a convenience store with flats above in Thamesmead.
Part of the ground floor shop was destroyed by fire. Five people were evacuated by crews, when they arrived on scene, from the flats above the shop via an internal staircase.
The Brigade's 999 Control officers were first called at 0216 and mobilised crews from Plumstead, East Greenwich, Erith, Eltham, Bexley and Lee Green fire stations. The fire was under control by 0455.
The cause of the fire is under investigation.