Herein we report a nickel-catalyzed cross-electrophile ring-opening reaction of vinyl epoxides wherein aryl iodides, alkyl iodides, and benzyl chlorides can all serve as the electrophilic coupling partners, providing a new approach to preparing multisubstituted allylic alcohols. This new method features broad substrate scope (76 examples), good step-economy, and high L/B- and E/Z selectivity as well as mild reaction conditions.