Rovers, who had won their last five games, would have leapfrogged Catalan into fifth spot in the Super League standings if they had pulled off victory at under-strength Warrington.
That still looked a possibility at half-time with Warrington fortunate to be 12-6 ahead through from tries from Brett Hodgson and Mike Cooper, who both went over early on before Jordan Cox replied for Hull KR.
But the Wolves took the game away from their opponents after the break with four unanswered touchdowns, two from Ben Currie and others from Chris Riley and Michael Monaghan, to secure the victory. Hodgson also finished with four goals to go with his opening try.
The Wolves, who face Hull at Huddersfield in the Challenge Cup semi-final next Sunday, rested captain Adrian Morley, Ben Westwood, Stefan Ratchford, Paul Wood and Simon Grix with Richie Myler and Ryan Atkins out injured.
Ben Harrison returned from a three-month injury absence for Warrington, who included Brad Dwyer after his loan spell at Huddersfield.
Rovers, who had lost their last four clashes at Warrington since 2008, handed Tyla Hepi his debut off the bench and brought back Sean Gleeson with Cory Paterson and Alex Brown out.
The visitors almost took an early lead with Travis Burns just failing to reach a Craig Hall kick after the stand-off had started the move with a superb pass.
It was Warrington who went in front though following a strong burst by Garreth Carvell, with Chris Bridge’s kick bouncing kindly for Hodgson to touch down after six minutes with the full-back adding the conversion.
The Wolves stretched the advantage to 12-0 in the 13th minute when Cooper blasted through Constantine Mika’s tackle.
Burns made a lively start for Rovers and his pass allowed Cox to round Hodgson to go over to reduce the deficit, with Michael Dobson converting to score for his 13th match in a row against Warrington – a run stretching back five years.
Josh Hodgson had a try disallowed for Hull KR who had started to come back strongly after a poor start.
Rovers were bidding for a notable double after a 26-12 home win in March but would have fallen further behind had Warrington opted not to run a straightforward penalty in front of the post just before the break.
Burns then had a touchdown ruled out by referee Tim Roby for a forward pass with Warrington ahead 12-6 at the interval.
Rhys Williams spilled a Hodgson pass early in the second half to squander a try opportunity before Lee Briers tossed away another chance by kicking ahead when in the clear.
Briers had rounded Greg Eden but lacked the confidence to finish off the move, but he made amends by sending Currie over in the corner after a Bridge breakaway.
Hodgson missed the touchline conversion but Warrington still led 16-6 after 52 minutes.
Greg Eden was stopped by Currie and Briers as Rovers attempted to fight back but a solo try from Riley 17 minutes from time calmed Warrington’s nerves.
Riley mesmerised several defenders with Hodgson’s goal stretching the lead to 22-6.
Rovers’ hopes were finally dashed with Lincoln Withers missing a vital tackle to allow Monaghan to scamper over near the posts.
Currie bagged his second try six minutes from time as Rovers ran out of steam.
Warrington Wolves: Hodgson, C Riley, J. Monaghan, C Bridge, Williams, Briers, M Monaghan, Carvell, Higham, Hill, Waterhouse, Currie, Cooper. Substitutes: Dwyer, Harrison, McCarthy, G. Riley.
Hull KR: Eden, Hall, Gleeson, Salter, D. Hodgson, Burns,Dobson, Paea, J. Hodgson, Walker, Lovegrove, Cox, Mika. Substitutes: Withers, Beaumont, Hepi, Tuimavave.
Referee: T Roby (RFL).