Wallen, 27, was pulled from the show after violating coronavirus safety protocols. He was filmed at a party in Alabama, socialising with other guests while not wearing a mask.
Wallen apologised and called his behaviour “short-sighted”.
SNL executive producer Lorne Michaels has now confirmed White will appear instead.
“It probably isn’t the first country singer, the first person from rock and roll, who partied after, in that case, a football game,” Michaels told NBC’s Today show.
“But we’re just living in a different time and everything is scrutinised.”
Wallen issued a video apology after being booted from his SNL spot.
The Tennessee-born singer, whose hits include More Than My Hometown, Whiskey Glasses and 7 Summers, said he has “some growing up to do” after being distracted by his success.
White, best known as the lead singer and guitarist of the duo The White Stripes, will be making his third solo SNL appearance as a musical guest, and fourth overall.
The White Stripes Greatest Hits collection will be released in December.
This week’s SNL host is the comedian Bill Burr.
