Cross‐electrophile coupling reactions are efficient for the construction of carbon‐carbon bonds under relatively mild conditions, and hence widely used for making new molecules. Among various electrophiles, the cross‐electrophile coupling reaction between two different tosylates has been rarely studied. Herein, we present a cross‐electrophile coupling of gem‐difluoroalkenyl tosylate (C(sp2)−OTs) and α‐CF3 benzyl tosylate (C(sp3)−OTs) by nickel/palladium cooperative catalysis. Mechanistic investigation indicated that the activation of C(sp2)−OTs bond and C(sp3)−OTs bond was facilitated by nickel and palladium respectively. A cross‐electrophile coupling reaction of gem‐difluoroalkenyl tosylate with α‐CF3 benzyl tosylate is presented. This protocol is the first example of cross‐electrophile coupling between two different tosylates by Pd/Ni cooperative catalysis.