Nozaki–Hiyama–Kishi reaction has been widely applied in the functionalization of carbonyl compounds with the help of Ni catalysis. Herein, a divergent regio- and stereoselective diarylation of dienes has been developed under Ni/Cr cocatalysis without the inherent driving force for the formation of polar metalalkoxides. Preliminary experimental studies have been conducted to elucidate the key roles of Ni, Cr