The construction of fully substituted carbon centers remains a challenge for modern C(sp 2 )-C(sp 3 ) radical crosscoupling. Often, the answer to this challenge is not a straightforward application of existing methods that excel at coupling primary and secondary alkyl partners. Inspired by this, we sought to develop a metallaphotoredox method for decarboxylative C(sp 2 )-C(sp 3 ) cross-coupling of tertiary carboxylic acids with aryl halides (Figure ). Initial attempts with traditional bipyridyl-based Ni-catalysts led to trace product formation and a significant amount of ester byproduct. By employing high throughput experimentation (HTE), we identified Ni(TMHD)2 as a suitable catalyst that promotes the desired tertiary cross-coupling selectively with complete suppression of the esterification reaction. As depicted in Figure , we proposed that our cross-coupling follows a mechanism similar to what has been described for other related tertiary alkyl systems. DFT studies support that an outer sphere reductive elimination process between Ni(TMHD)ArX and the tertiary alkyl radical delivers the cross-coupled product.