Six fire engines and 35 firefighters and offices were called to a fire in a second floor flat on Notting Hill Gate.
Station Manager John Ryan said: "When crews arrived they were could see flames coming out of the window of a flat on the second floor. Firefighters wearing breathing apparatus rescued a man via an internal staircase from the flat affected. He has been taken to hospital by London Ambulance Service crews.
"A woman was also rescued from a third floor window via aerial ladder platform. Around 30 residents self evacuated from the block."
The Brigade’s 999 control centre took 12 calls to the visible blaze.
The Brigade was called at 0900 and the fire was under control by 1045. Fire crews from Kensington, Paddington, North Kensington and Hammersmith fire stations attended the scene.
The cause of the fire is under investigation.