The 'Le Freak' band performed a set packed with their greatest hits at Barclaycard British Summer Time in Hyde Park, ending the performance with a star-studded stage invasion.
As well as the 22-year-old supermodel and the 'Stay With Me' hitmaker - who previously worked with Nile on Disclosure's 'Together' - U2's The Edge, 'Strictly Come Dancing' and 'Dancing with the Stars' judge Bruno Tonioli and a series of other people crowded around the disco icon and his band.
After the concert, Sam Smith gushed on Instagram, writing: ''LOVED seeing one of my favourite people today!! @nilerodgers!! Every time I see you perform it brings me so much happiness x love you sir x (sic).''
The 47-year-old star arrived on stage in a floral crown and fur-lined cape, treating the 60,000-strong crowd to three further costume changes, including a red sequinned minidress, a strapless silver jumpsuit and a tuxedo-inspired leotard complete with diamond jewellery.
Aside from her eye-catching outfits, Kylie - who has been singing for more than 25 years - performed some of her greatest hits including 'Better the Devil', 'Wow', 'Can't Get You Out of My Head' and 'Spinning Around'.
The musician also threw back to the beginning of her career by prompting a sing-a-long to the theme tune of Australian soap 'Neighbours', on which she began her showbiz journey.
Barclaycard British Summer Time continues on Friday (26.06.15) when The Who will perform along with Kaiser Chiefs and Paul Weller, while Taylor Swift will headline on Saturday (27.06.15) with support from John Newman and Ellie Goulding.
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