The anchor store will occupy a 103,000 sq ft (9,570 sq m) three-level space in the southeast corner of the redevelopment.
The signing of House of Fraser completes the letting of Westfield's six anchor stores.
Other big retailers in the scheme include Marks & Spencer, Debenhams, Waitrose and Next, who will each create a flagship store alongside 265 smaller retail units and a wide selection of cafés, restaurants and brasseries.
The project is a joint venture with CGI and will act as a catalyst for the wider regeneration of the White City area, with a further£1 billion investment expected over the next 10 years.
House of Fraser executive chairman Don McCarthy said: 'We have been selectively looking at opportunities where we can find our niche and growth potential in the market and we believe that the combination of the demographics and the scheme will be an excellent choice for House of Fraser.'
Westfield UK & Europe managing director Michael Gutman said: 'This development will be the capital's most exciting premium fashion, lifestyle and leisure experience when it opens in the autumn of 2008. Its unique trade area presents a first class opportunity for the future of our retailers.'
CGI managing director Frank Pörshke said: 'We are delighted to have attracted such a strong line-up of pre-eminent retailers to the scheme. This line-up confirms the demand for high-quality, well-located and well-designed retail space in this part of west London.'
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