The 27-year-old, who will feature for his country at the World Cup, has joined the newly promoted Premier League side on a temporary deal for the 2018-19 campaign.
Jimenez started only six of his 33 league appearances for Benfica last season, scoring six times, and will now seal his move subject to international clearance and a work permit.
Wolves' signing of Jimenez has allowed the club to move another striker out on loan, with Benik Afobe heading to Stoke City.
The former Bournemouth striker only joined Wolves permanently at the start of the month, but has now signed for the relegated Potters, where there is an obligation to make the move permanent in January.
Gary Rowett's side will reportedly pay £12.5 million ($17m) for the front man, who scored six goals for Wolves last season.