Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising:(a) reacting said saturated hydrocarbons of the formula:RH where:H represents a hydrogen atom, andR represents a saturated hydrocarbon radical, with a metal complex of the formula:CpRhPMe.sub.3 H.sub.2 where:Cp represents a pentamethylated cyclopentadienyl radical,Rh represents a rhodium atom,P represents a phosphorous atom,Me represents a methyl group,H represents a hydrogen atom, in the presence of ultraviolet radiation at a temperature maintained at about -60.degree. to -17.degree. C. to form a hydridoalkyl complex of the formula:CpRhPMe.sub.3 RH(b) reacting said hydridoalkyl complex with a haloform of the formula:CHX.sub.3 where:X represents a bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula:CpRhPMe.sub.3 RX; and,(c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e. ambient) to form a functional haloalkyl compound.