The 27-year-old Rondon went 2-3 with an 8.49 ERA and one save in 35 games with Chicago. The right-hander got one out and issued three walks in Tuesday night's 14-2 loss to St. Louis.
Manager Rick Renteria said Rondon "wasn't throwing enough strikes."
The White Sox also purchased the contract of righty Jeanmar Gomez from Triple-A Charlotte before their game against the Cardinals on Wednesday night.
The 30-year-old Gomez was 5-0 with a 2.03 ERA and two saves in 30 relief appearances with Charlotte. He was 3-5 with 37 saves with Philadelphia in 2016.