Former Rotherham loanee Nouha Dicko and Kieran Agard each grabbed a hat-trick but it was the home side who would eventually take victory amid scenes of great drama at Molineux, with Wolves winning a stunning contest 6-4.
Dicko’s double cancelled out Agard’s opener then Dave Edwards put the leaders 3-1 in front but the in-form Millers striker pulled one back.
Dicko then hit his third with ten minutes remaining but Rotherham kept battling and Joe Skarz snatched another for Millers in an enthralling League One clash.
Agard sealed his third with two minutes remaining but in the 90th minute Ricketts scored the fifth for Wolves and deep into injury time Kevin McDonald made it six to finally kill off Rotherham.
There was a ten minute delay to kick off due to traffic problems on the M1.
Rotherham boss Steve Evans made just one change to the side which drew 0-0 with Bradford last week, with Haris Vuckic coming in for Ben Pringle who dropped to the bench.
Wolves named an unchanged line-up from the team which won away at Crewe on Saturday.
After the delay, it was the home side who started better and in the third minute Richard Stearman perhaps should have opened the scoring but headed over from close range.
However, after Sako had dragged a shot wide of goal Millers rallied and began to exert pressure of their own.
That bore fruit on 14 minutes when first of all Michael O’Connor’s free kick eventually found Adams whose shot was deflected away for a corner.
From there, again O’Connor took the set piece and this time found Agard who glanced his header inside the far post.
The lead didn’t last too long though as six minutes later Wolves were level.
Rotherham thought they had won a throw in but it was awarded to the home side. Sako then picked up the ball and crossed for Dicko who knocked home.
There was little in the way of goalmouth action after that equaliser until once again Dicko struck to complete the turnaround.
Again Sako was the provider, crossing for the unmarked Dicko, giving the French striker the opportunity to fire home from the middle of the box.
Millers were left stunned by that and lifted by a sold out home crowd, Wolves went further ahead on 38 minutes as Scott Golbourne went on a great run and played in Edwards who dispatched past Collin in the Rotherham goal.
Wolves made a change at the break as James Henry replaced Lee Evans but it was the Millers who had the first chance of the second half as Vuckic made space for himself but saw his effort tipped away by Ikeme.
From the corner Vuckic had another chance as O’Conner’s set piece was put back into the danger area by Morgan but the Slovenian headed straight at the Wolves keeper.
Rotherham continued to press; Adams fired well over with a half chance before he turned provider for Arnason who glanced a header wide of goal.
Then just after the hour mark, the pressure told as O’Connor crossed for Agard who bided his time, showing neat feet before finally firing home.
On 66 minutes Wes Thomas came on for Alex Revell and a minute later Rotherham had another chance as Morgan’s header was saved by Ikeme after Adams had fored in a corner.
Wolves remained dangerous going forward and Dicko could have had his hat trick on 68 minutes but his effort was saved by Collin.
Both sides then made substitutions in quick succession as Rotherham brought on Ben Pringle for Vuckic and then Wolves replaced Sako, who was dangerous in the first half but quiet after the break, with Jack Price.
On 77 minutes as Millers pushed forward Wolves almost sealed the win when Sam Ricketts burst down the right and cut inside but saw his shot cannon off the post.
However two minutes later the fourth finally arrived and unsurprisingly it was Dicko who grabbed the goal.
Edwards claimed the assist as he took a pass from henry and crossed for Dicko who fired home from just inside the six yard box.
The goals didn’t end there and with six minutes remaining Joe Skarz connected with an Adams cross to keep Rotherham in the game and set up a frantic finish.
Agard then sensationally scored the second treble of the day as he converted James Tavernier’s pass but the next goal would go to the home side as in the last minute of normal time Edwards fed Ricketts who fired into the top corner.
Then in the seventh minute of injury time with Millers pressing for another equaliser, Wolves broke through Dicko and the hat-trick hero passed to McDonald who finally brought the curtain down on a memorable game in the Black Country.
WOLVES: Ikeme, Ricketts, Batth, Stearman, Golbourne, McDonald, Evans, Jacobs, Edwards, Sako, Dicko. SUBS: McCarey, Ebanks-Landell, Doherty, Price, Henry, McAlinden, Clarke.
ROTHERHAM: Collin, Skarz, Arnason, Revell, O’Connor, Morgan, Agard, Tavernier, Vuckic, Smallwood, Adams. SUBS: Shearer, Brindley, Davis, Milson, Pringle, Thomas, Hitchcock.