The hosts suffered a first defeat of the campaign last weekend after making a perfect start, while their visitors managed a first victory at home to Huddersfield Town on Saturday.
Match preview
Charlton head into the weekend aiming to reignite a fast start to their League One campaign, having headed into a first full season under the management of Nathan Jones with plenty of optimism.
Seeking to challenge for promotion after Jones inspired a climb away from the threat of the drop in a tough campaign last time around, the Addicks enjoyed a dream start, winning each of their first three games in England's third tier having firstly seen out 1-0 victories over Wigan Athletic and Leyton Orient.
A tough test at home to Bolton Wanderers then followed and Jones's men made no mistake in extending their hot streak, picking up a 2-0 victory courtesy of goals from Greg Docherty and Matt Godden and a third straight clean sheet.
Jones's men then visited Reading last time out and saw that run come to an end, having conceded their first league goal of the season to a Charlie Savage strike around the hour mark before Sam Smith doubled the hosts' lead 14 minutes from time.
Still with plenty of positives to take from their fast start, Charlton Athletic will now bid to bounce back and make it four victories and 12 points from the first five outings in their promotion bid.
They face another tough test, though, as the visitors arrive aiming to make it back-to-back wins to move closer to the leading pack.
Following a dismal Championship campaign last time around, Rotherham United dropped back into League One under the management of Steve Evans with the aim of making a swift return to England's second tier, but they had to endure a slow start.
Indeed, the Millers failed to score a single goal in their first three outings, with the only point coming from a stalemate against Bristol Rovers either side of losses to Exeter City and Wycombe Wanderers, before heading into a tough test against Yorkshire rivals Huddersfield Town, who boasted a perfect record from their first three matches, last weekend.
That game remained goalless for 74 minutes before the visitors went ahead through Joe Hodge soon after being reduced to 10 men, but the Millers would quickly restore parity through a Jonson Clarke-Harris penalty before Mallik Wilks fired them to a first league victory of the campaign with a decisive injury-time goal.
Now facing a tough trip to the Valley, Rotherham United will be keen to build on last week's crucial win and further kickstart their promotion push with another three points on Saturday.
Charlton Athletic League One form:
W
W
W
L
Charlton Athletic form (all competitions):
W
W
L
W
W
L
Rotherham United League One form:
L
D
L
W
Rotherham United form (all competitions):
W
D
W
L
L
W
Team News
Nathan Jones may opt to make several alterations to his Charlton Athletic starting XI after last week's 2-0 defeat to Reading, with plenty of options to call on throughout the pitch.
Tyreece Campbell and Gassan Ahadme have been preferred up front in each of the Addicks' four league outings so far, although Matt Godden, Chuks Aneke and Daniel Kanu all have claims to come in from the outset.
Allan Campbell will hope to earn a debut in midfield following his loan arrival from Luton Town but faces stiff competition from Conor Coventry and fellow summer arrivals Luke Berry and Greg Docherty, while Ale Mitchell, Lloyd Jones and Macaulay Gillesphey should again line up in a back three.
After picking up a first league victory of the season last time out, Rotherham United could be unchanged for Saturday's trip, with defenders Sean Raggett and Joe Rafferty remaining out of action due to injuries.
Captain Jonson Clarke-Harris, who opened his account for the season in their win over Huddersfield will again lead the line, likely alongside Sam Nombe, while Mallik Wilks will play an important role in support having won the levelling penalty and scored the winning goal in that game.
Elsewhere, Hakeem Odoffin could again fill in on the right-hand side of a back four with Liam Kelly, Christ Tiehi and Joe Powell getting the nod in midfield.
Charlton Athletic possible starting lineup:
Mannion; Mitchell, Jones, Gillesphey; Ramsay, Coventry, Docherty, Berry, Small; Godden, Ahadme
Rotherham United possible starting lineup:
Phillips; Odoffin, Humphreys, McCart, James; Kelly, Tiehi, Powell; Wilks; Clarke-Harris, Nombe
We say: Charlton Athletic 1-1 Rotherham United
The two teams both boast an abundance of quality, and we anticipate a high-quality and close-fought encounter at the Valley.