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The brigade said 18 fire engines and more than 100 firefighters were called to the blaze in the Camberwell area of south London at around 4:20 p.m. (1520 GMT).
The fire started on the fourth floor and spread quickly to seven floors of the 12-story building, part of a large 1960s public-housing project.
"It was shocking to see the quantities of smoke and flames," said Sarah Gresty, who lives nearby.
The brigade said 30 residents had been rescued from the building "in extremely difficult circumstances."
The London Ambulance Service said 16 people had been taken to local hospitals, most suffering from smoke inhalation.
Four hours after it began, the fire brigade said the blaze was under control and investigators were on the scene to determine its cause.
Written and photos by Associated Press