The Premium Store includes denim, lingerie, dresses and outwear products.
The move follows speculation that Amazon would make aggressive moves into the fashion market with a bid for online retailer Asos.
Rival online pure-play retailer eBay has already made inroads into fashion and, in the summer, signed a multi-season sponsorship deal with the British Fashion Council's (BFC) Fashion Forward Initiative, which supports emerging design talent.
Jessica Brown, head of fashion at Amazon UK, said: "The new store brings together the latest, must-have women's fashion brands and marks the introduction of some of our favourite US denim brands at Amazon.co.uk.
"In addition to big-name labels like 7 For All Mankind, the store also offers cult denim labels such as Siwy, giving customers a great breadth of designer styles to choose from."
The launch of the store comes at a time when Amazon is coming under increasing pressure to restructure its complex company structure that allowed Amazon.co.uk to pay just £1.8m in corporation tax last year on profits of £74m.
Starbucks has already bowed to pressure and has revealed it is reassessing the amount of tax it pays in the UK, saying it understands "we need to do more to maintain and further build public trust".Follow @mattchapmanuk