To selectively obtain a hydrogen-containing chlorofluorocarbon which is useful as a substitute for chlorofluorocarbon whose production and use have been prohibited due to its anxiety about ozonosphere disruption without the formation of by-products whose handling is troublesome.

This hydrogen-containing chlorofluorocarbon represented by the formula: Rf-CHCl2 is prepared by reaction of a halogenated hydrocarbon represented by the formula: Rf-CCl3 (Rf is a polyfluoroalkyl), for example, CF3CCl3 with a hydroxy compound of ROH (R is H, an alkyl), for example, methanol in the presence of a ruthenium catalyst (containing metallic ruthenium as an essential component) and/or a copper catalyst (containing a copper compound as an essential component). The catalyst used in the reaction is preferably supported on a carrier such as alumina, zirconia or an activated carbon.