Abstract: The invention relates to a process for preparing pentafluoroethane (R 125) by reacting perchloroethylene with hydrogen fluoride in the gas phase over a chromium-containing catalyst, wherein the catalyst used comprises chromium and magnesium and is obtainable by reacting a water-soluble chromium(III) salt with magnesium hydroxide or magnesium oxide and, if desired, graphite in the presence of water, converting the reaction mixture into a paste, then drying the paste and treating it with hydrogen fluoride at temperatures of from 20.degree. to 500.degree. C., using such amounts of chromium(III) and magnesium salts and, if desired, graphite that the dried paste before treatment with hydrogen fluoride contains from 4.5 to 26% by weight of Cr, expressed as Cr.sub.2 O.sub.3, and at least 25% by weight of Mg, expressed as MgO, and, if desired, graphite.