Eight fire engines and around 60 firefighters tackled a flat fire on Warrington Crescent in Maida Vale.
Part of a flat on the second floor was damaged by fire.
Nine people were rescued from the block by firefighters wearing breathing apparatus. Four people from the third floor, four people from the second floor and one person from the first floor. London Ambulance Service crews assessed them for smoke inhalation.
A further fifteen people self evacuated from the building before the Brigade arrived.
Firefighters used fire escape hoods to rescue the four people from the second floor.
Fire escape hoods provide members of the public with up to 15 minutes protection from four of the main fire gases (carbon monoxide, hydrogen cyanide, hydrogen chloride and acrolein) and can be worn by conscious or unconscious people. If more than 15 minutes protection is required then another hood can be given to each wearer. They do not provide oxygen but temporarily filter toxic smoke to make breathing easier.
The Brigade was called at 0618 and the fire was under control by 0740. Fire crews from Paddington and surrounding fire stations were at the scene.
The cause of the fire is under investigation by the Brigade and the Metropolitan Police Service.