The Sunweb pocket rocket and the Dutchwoman survived the double ascent of the Newnham Hill climb to contest the sprint out of a 18-rider lead group after 145 kilometres in the saddle.
The Californian rode much of the finale in Vos' slipstream, coming around her left side at the ideal moment, her epic bike throw ensuring stage victory and the race lead.
But it wasn't all plain sailing for Rivera when reigning OVO Energy Women's Tour champion Kasia Niewiadoma (Canyon SRAM), Vos (Waowdeals) and Elisa Longo Borghini (Wiggle High5) slipped off the front after the first climb of Newnham Hill, 35 kilometres from the finish.
But Rivera's team, particularly Floortje Mackaij, worked hard to bring back the leaders.
"We weren’t represented so did have to do something but we didn’t panic," Rivera said.
"I just communicated to Floortje, who was riding really well today, to help me pace it. Then as we got closer to the top I was able to bridge across to the climbers in the front group. Luckily we already had Ellen [Van Dijk] in there and so I just communicated to her to just drive it."
Van Dijk's efforts kept the front group together and warded off further attacks to set up the thrilling finish.
The race returns to Warwickshire with stage three's 150 kilometre trip from Atherstone to Royal Leamington Spa.