Process for functionalizing saturated hydrocarbons comprising:(a) reacting said saturated hydrocarbons of the formula:R.sub.1 H wherein H represents a hydrogen atom; and R.sub.1 represents a saturated hydrocarbon radical, with a metal complex of the formula:CpRh[P(R.sub.2).sub.3 ]H.sub.2 whereinCp represents a cyclopentadienyl or alkylcyclopentadienyl radical;Rh represents a rhodium atom;P represents a phosphorus atom;R.sub.2 represents a hydrocarbon radical;H represents a hydrogen atom, in the presence of ultraviolet radiation to form a hydridoalkyl complex of the formula:CpRh[P(R.sub.2).sub.3 ](R.sub.1)H(b) reacting said hydridoalkyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas:CX'X''X'''X'''' or CHX'X''X''' wherein X', X'', X'", X"" represent halogens selected from 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.