Rouse is expected to advise clients on navigating their initiatives through Washington in his role at Perkins Coie, a person familiar with the situation told the Washington publication.
It wasn't clear when Rouse would leave.
Rouse served as former Senate Majority Leader Tom Daschle's chief of staff and was going to retire before Obama entered the Senate. Rouse then worked for Obama as his Senate chief of staff.
After Obama's election as president, Rouse moved to the White House and was an interim chief of staff after Rahm Emanuel left to run for Chicago mayor.
The Hill also reported other changes in Obama's staff, including the departure Wednesday of Miguel Rodriguez as director of White House Legislative Affairs office. Katie Beirne Fallon is his successor.
As previously reported, Ed Pagano, who led the White House's Senate team, is expected to leave the administration soon for a Washington law firm, a source told the Hill. He will be replaced by Anne Wall, who worked in the White House legislative affairs office for two years.