Four fire engines and around 25 firefighters were called to a flat fire on Cheval Place in Knightsbridge.
Part of a five-roomed flat on the third floor of the building was damaged by fire. Most of the external decking of a flat was also damaged by the blaze. Ten people left the building before the Brigade arrived. There were no reports of any injuries.
The Brigade's Fire Investigators believe the fire was accidental and involved a shisha pipe.
Sub Officer Edwards, who was at the scene, said: “As we arrived, there was a black plume of smoke coming out from the top of the building.
“The fire had started on a balcony and spread into the flat. Crews accessed the roof space above the flat and worked incredibly hard to bring the fire under control and stop it from spreading further.”
The Brigade was called at 0515 and the fire was under control by 0626. Fire crews from Chelsea, Kensington and Soho fire stations attended the scene.