Four fire engines and around 25 firefighters tackled a flat fire on Wood Lane in Shepherd’s Bush.
A studio flat on the third floor of a residential block was destroyed by fire. A man and a woman were taken to hospital by London Ambulance Service crews. A further 26 people left the building before the Brigade arrived.
A London Fire Brigade spokesperson said: “This incident shows just how important it is to have working smoke alarms in your home. There were smoke alarms fitted inside the affected flat which raised the alarm.
“Smoke alarms give the earliest possible warning when a fire starts, providing time to escape. We encourage everyone to have smoke alarms fitted in every room where a fire could start, plus a heat alarm in the kitchen. It's important to test them regularly.
“You can take a look at our new online Home Fire Safety Checker to get tailored fire safety advice for your home.”
The Brigade was called at 0401 and the fire was under control by 0541. Fire crews from North Kensington, Hammersmith and Kensington fire stations attended the scene.
The cause of the fire is under investigation.