Tom Briscoe responded for Hull, but the third of Michael Dobson's four kicks stretched Rovers' lead to 14-4.
The Robins started brightly as Ben Galea, Ben Fisher and Peter Fox crossed with Michael Dobson adding the extras.
Danny Orr gave Cas the lead before Michael Dobson and retiring captain Michael Vella put the hosts in front.
Michael Dobson made amends for his two missed kicks in the first half, with four successful efforts in the second.
Michael Dobson and Ben Galea restored the home lead by half-time, only for Luke Dorn and Lee Mitchell to again redress the balance.
The Rhinos trailed 14-6 early in the second half after Kris Welham and Ben Cockayne crossed for Rovers and Michael Dobson kicked three goals.
From the resulting scrum, Daniel Fitzhenry sidestepped through for a try which was given by the video referee and Michael Dobson added the extras.
Astonishingly, Rovers then went 6-4 ahead, centre Kris Welham pouncing on Michael Dobson's kick, the scrum-half then succeeding where Eastmond had failed with his conversion attempt.
But, when Schifcofske missed a high up-and-under on the sixth tackle, Rovers winger Peter Fox was in at the corner, Michael Dobson levelling with a touchline conversion.
The interchange burst into Warrington's half before offloading inside to Michael Dobson, who sent the killer pass out to the New Zealander to touch down an exhilarating try.
First they repelled a wave of Warrington attacks, then, with their first real foray into Wolves territory, got on the board when Green's grubber kick was pounced on by Newton to touch down, Michael Dobson converting.
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