The synthesis of perfluorocarbons (PFC) and hydrofluoroethers (HFE) using CAVE method was studied. The in-situ fluorination using the CAVE was conducted with hydrocarbons, hydrofluorocarbons, ethers and low F-containing hydrofluoroethers. Effects of the reactant species, the reaction temperature, the feed ratio of F₂ generated/reactant, and the current density of the carbon anode on the yield and the selectivity of PFC or HFE were evaluated. The targeted highly fluorinated materials were successfully produced, but the production rate was limited by the gas flow through the porous carbon anode. The production of by-products and the polarization rate of the carbon anode were mainly affected by the reactant species; the selectivity of PFC or HFE was improved by using partially fluorinated reactants, but the use of reactants having double bonds produced more by-products and accelerated the polarization of the carbon anode.