Two-time US Open winner DeChambeau carded a seven-under-par 64 on another low day of scoring for a tournament total of 21 under par, putting him two shots ahead of South Africa's Branden Grace.
Southern Guard, made up of Grace and compatriots Louis Oosthuizen, Dean Burmester and Charl Schwartzel, lead the team competition on a cumulative total of 60 under par ahead of Fireballs and overnight leaders Torque, who are both on 58 under.
The first LIV Golf event on African soil is expected to draw over 100,000 people over the four days, with the weekend sold out at the Jack Nicklaus-designed par-71 course.