Like Daisy, Game Of Thrones star Emilia Clarke added a pop of colour to proceedings, standing out from the black tie wearing crowd in her bright orange strapless dress and strappy heels.
Before Pixie arrived, the evening's presenter Samuel L Jackson made his big entrance Although Pixie was the star the red carpet as she arrived at London's Royal Opera House for the star-studded event, she stop to pose with her long-term boyfriend, model Oliver Cheshire.
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Low cut and supershort, the showstopping piece was a £2,145 velvet tuxedo dress by Balmain - a French label adored by the Kardashians among others.
However, a representative for Horan later scotched the rumours, telling MailOnline: 'They're not dating, they're just friends.
The men were also represented, with the red carpet seeing a series of talented gents walk along its length, among them Sam Smith, who will perform the new Bond theme tune.