In this paper we show the C–F bond activation and alkylation in polyfluoroaryl imines. An active trimethylphosphine supported nickel-catalyzed cross-coupling reaction of polyfluoroaryl imines with ZnMe2 under mild conditions is described. According to the in situ19F NMR spectroscopic data, the substrates are quantitatively converted into di- methylation products, while mono-methylation can also be realized under the controlled ...