The fire is believed to have broken out in the Mandarin Oriental Hotel near the Capital's West End.
It comes just weeks after the luxury hotel completed an extensive renovation.
Speaking from the scene, LondonFire Brigade Station Manager Pam Oparoacha had said: "The smoke from this large fire was very visible across central London this afternoon and we received a number of emergency calls".
More than 100 firefighters are tackling a blaze through the five-star Mandarin Oriental Hotel, and singer Robbie Williams has been recorded being evacuated from the premises.
No casualties have been reported at time of writing.
"This is actually happening", a hotel guest wrote, posting a video which saw many fleeing down the fire escape from the burning building.
Another worker, who asked not to be named, said: "The fire alarm started and everybody was told to get outside".
Both the ambulance service and the Met Police are also attending the scene, although there are no reports of any injuries, the fire brigade said.
Plumes of thick, black smoke were seen billowing into the air above Hyde Park, as traffic in the area was brought to a standstill.
"Just evacuated Mandarin Oriental hotel to see this... absolutely insane!" Firefighters were called to the fire at 1455 GMT.
After the blaze broke out, staff were evacuated from the 12-storey building to Hyde Park, where they were given bottles of water.
A Mandarin hotel group spokeswoman said that work on the building was still being carried out.
The hotel says it is "aware of a situation".
Various launch events starting next week were going to unveil the 18-month project.
Fire crew from Chelsea, Kensington, Hammersmith, Battersea and other surrounding fire stations are at the scene.
The Mandarin Oriental has had a long relationship with the Royal Family and it hosted a gala dinner before the wedding of the Duke and Duchess of Cambridge in 2011.
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