The present application provides a hydrodefluorodimerization process, which is useful in the synthesis of, for example, fluoroölefins that can be used as refrigerants, blowers and the like. The process is an “early-stage fluorination” process, wherein precursors containing fluorine are assembled into the desired product using a zerovalent nickel catalyst. Also provided is a liquid composition comprising one or more fluoroölefin produced by this catalytic process.