Trifluorovinylzinc is a common synthetic intermediate for trifluorovinyl derivatives, including α,β,β-trifluorostyrenes and hexafluorobutadiene. Here, we report a novel synthetic approach for the formation of trifluorovinylzinc chloride via a C–F bond activation of tetrafluoroethylene (TFE), which is an industrially cost-effective bulk feedstock with a negligible GWP. The present system provides a practical synthetic route to various trifluorovinyl derivatives with very low energy consumption.