A practical nickel- and photoredox-catalyzed Csp³‒H monofluoroalkenylation with tetrasubstituted gem-difluoroalkenes to the synthesis of tetrasubstituted fluoroalkenes with complete control of stereoselectivity has been developed. Moreover, the gem-difluoroalkenes also can undergo photoredox-catalyzed cascade twofold C‒F diaminomethylation.