Three photochemical reports show that tertiary alkyl radical precursors can be cross-coupled with aryl halides, and Ni(TMHD)2 complex is the only effective catalyst in those three photochemical reports. While effective at promoting the formation of quaternary centers, a noticeable drawback of Ni(TMHD)2 complex in those cross-couplings is its incompatibility with ligating substrates such as bromopyridine and other simple (hetero)aryl halides; doping experiments showed that pyridine and other heterocycles inhibit the active Ni-species in related cross-coupling reactions. In contrast, the electrochemical method presented in this report overcomes these limitations, as exemplified by compounds 16, 21, and 27. Furthermore, a vast collection of (hetero)aryl halides can be employed as suitable coupling partners (Figure ).