A process for the manufacture of CF.sub.3CH.dbd.CHF and/or CF.sub.3CF.dbd.CH.sub.2 is disclosed. The process involves (a) reacting HF and chlorine and at least one halopropene of the formula CX.sub.3CCI.dbd.CCIX (where each X is independently F or Cl) to produce a product including both CF.sub.3CCI.sub.2CCIF.sub.2 and CF.sub.3CCIFCCI.sub.2F; (b) reacting CF.sub.3CCI.sub.2CCIF.sub.2 and CF.sub.3CCIFCCI.sub.2F produced in (a) with hydrogen to produce a product including both CF.sub.3CH.sub.2CHF.sub.2 and CF.sub.3CHFCH.sub.2F; (c) dehydrofluorinating CF.sub.3CH.sub.2CHF.sub.2 and CF.sub.3CHFCH.sub.2F produced in (b) to produce a product including both CF.sub.3CH.dbd.CHF and CF.sub.3CF.dbd.CH.sub.2; and (d) recovering CF.sub.3CH.dbd.CHF and/or CF.sub.3CF.dbd.CH.sub.2 from the product produced in (c). In (a), both CF.sub.3CCI.sub.2CCIF.sub.2 and CF.sub.3CCIFCCI.sub.2F are produced in the presence of a chlorofluorination catalyst consisting of (i) compositions comprising a crystalline alpha-chromium oxide where at least 0.05 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by copper, and (ii) compositions of (i) which have been treated with a fluorinating agent.