The effect of the chromium-magnesium precursor preparation techniques on physicochemical properties (BET surface area, total pore volume, mean pore diameter) and catalysts activity in the gas-phase hydrofluorination of perchloroethylene to pentafluoroethane (Freon 125) was studied. Kinetics of the catalytic reactions was studied for the most active catalyst. Based on the experimental data, the pathway of perchloroethylene fluorination with HF was suggested.