Six fire engines and around 40 firefighters attended a fire at a care home in Hillingdon Road, Uxbridge.
A man and a woman were rescued by firefighters from the first floor, and taken to hospital by London Ambulance crews.
Part of the first floor was damaged by fire.
The Brigade was called at 0022 and the fire was under control by 0220.
Fire crews from Hillingdon, Hayes, Ealing and Ruislip stations attended the incident.
The cause of the fire is under investigation