It is understood the woman was hit by the wooden frames of a ground floor window in Hanover Street, Mayfair.
A witness told BBC London the woman was eating her lunch when she was struck on her chest.
London Ambulance and police were called at 11:30 BST. The woman, believed to be in her 20s, was treated at the scene but was pronounced dead by paramedics.
The building, 5 Hanover Square, is a multi-million pound development comprising six floors of office space. The ground floor is in the process of being turned into an art gallery.
Orla Wojtowitz said it "happened in a second" and it was impossible for the victim to have seen it happen.
"She was just passing and then she was suddenly lying on the pavement," she added.
Another witness, Beverley Hazel, said she was on her way to work in nearby Conduit Street at 11:30 BST when she saw a young woman "half lying in the road".
"A man was saying to her 'can you hear me?' but I don't think there was any response. It had just happened," she said.
"Then there was a lady who said she was a doctor. She got on with doing CPR and I counted three minutes for her."
Mrs Hazel, who lives in Kennington Oval, south London, said she believed the victim was hit by two "massive" wooden window frames, measuring about 10ft by 10ft.
"She was very young and slight. I've got two daughters, one younger and one older than this woman. I was in bits.
"If it had been my daughter I would have wanted someone with her.
"I went back later to lay some flowers."
The Health and Safety Executive is aware of the incident, police said.
London Ambulance said it sent two cycle responders, two ambulance crews and a hazardous area response team and an air ambulance to the scene.
Hanover Square has been closed between Brook Street and St George Street.
Bus routes 8, 25 and 55 have been diverted.
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