The Millers could move four points above the relegation zone with victory while also moving seven above the Addicks.
Here is an in-depth preview of the game.
Team news
Rotherham will add new signings Andrew Shinnie and Chris Dawson to their squad.
Shinnie is the more likely to start, though Neil Redfearn has a selection headache as to who he drops after an impressive performance at Cardiff last week.
Aimen Belaid is rated at 50/50 as he struggles with a groin injury and he will undergo a fitness test on Friday. Farrend Rawson is on standby to replace the Tunisian.
Lee Frecklington has suffered a set-back in his recovery from a hamstring injury, the same problem which looks like ruling Matt Derbyshire out.
Leon Best and Stephen Kelly are long-term injury absentees.
What the manager says
Millers boss Neil Redfearn has played down the importance of Charlton's visit, but admits it is a great chance for his side.
The opposition
Charlton will hope that the battling 1-1 draw with Blackburn last week represents the start of a resurgence under Jose Riga.
Prior to the Rovers clash, the Addicks lost Championship games at Huddersfield and Hull to an aggregate of 11-0 while also went out of the FA Cup to League One strugglers Colchester.
They are without a win in any competition in 12 games, stretching back to November 21 and cannot afford to lose against the Millers.
Forward Ademola Lookman is training again following his recent hamstring problems, but is not expected to be rushed back.
Belgian defender Patrick Bauer faces around a month out following surgery on a groin injury. Midfielders Alou Diarra (foot) and Ahmed Kashi (Achilles) both also continue their rehabilitation.
Things to look out for
Rising to the challenge
Rotherham's home form has been impressive in recent weeks, with a lop-sided 3-0 defeat to QPR last time out the only blip. So the Millers need to continue in that vein against a side with a horrid case of travel sickness and if they do match the level found against Hull, Bolton and Brighton then they should be celebrating three points. Things are never that easy when Rotherham are involved, though, and historically games like these, when victory is expected, usually ends in defeat. However, they can take strength out of delivering the goods against Bolton when they the favourites and they know if they can win it would leave Charlton needing to win three more games than the Millers to overhaul them.Who plays where?
Neil Redfearn's recruitment this month has been much-needed but also, on paper at least, perfectly judged. They have strengthened down the core of the side and now they have options in all areas, particularly midfield. And it leaves Redfearn with a selection headache. Does he play 4-4-2, which he would like to at home? With Derbyshire a doubt and Becchio not quite ready for a start, it would not be a surprise to see him go with just Danny Ward in attack, but who plays the 10 role? Grant Ward excelled at Cardiff last week but Andrew Shinnie is now available. It finally makes a nice change to have a plethora of choices instead of none.Pick your starting XI
Stats
Rotherham's last five games: LLWLD
Charlton's last five games: DLLLD
Head-to-head record against Charlton: P33 W14 D9 L10
Last time against the Addicks: 1-1, September 2015