The campaign, brokered by OMD and launching in November, will see breakfast DJ Robin Banks offering listeners the chance to win VIP packages to premier London nightclubs, as well as Rimmel goodie bags.
Rimmel London will also sponsor Kiss 100's What's On? Guide, which airs five times daily on Thursdays, Fridays and Saturdays.
The sponsorship will take the form of 30 and 60-second credits, while Rimmel will also have a presence at Kiss 100's residencies at London nightclubs and at its six-hour music mix special going out on New Year's Eve.
"Kiss 100 is one of the most dynamic youth brands in the UK and is consistently the most listened to station by London's youth," said Kurt Edwards, commercial director at Kiss.
Natalie Moon, UK marketing manager at Rimmel London, added: "The high profile Rimmel London has, with Kate Moss as our face, makes the association with Kiss 100 and its young urban listeners the perfect partnership."