Reactions of the ground-state titanium and zirconium monoxide and dioxide molecules with monochloromethane in excess argon matrixes have been investigated in solid argon by infrared absorption spectroscopy and density functional theoretical calculations. The results show that the ground-state MOx (M = Ti, Zr; x = 1, 2) molecules react with CH3Cl to first form the weakly bound MO(CH3Cl) and MO2(CH3Cl) complexes. The MO(CH3Cl) complexes can rearrange to the CH3M(O)Cl isomers with the Cl atom of CH3Cl coordination to the metal center of MO upon UV light irradiation (lambda < 300 nm). Theoretical calculations indicate that the electronic state crossings exist from the MO + CH3Cl reaction to the more stable CH3M(O)Cl molecules via the MO(CH3Cl) complexes traversing their corresponding transition states. The MO2(CH3Cl) complexes can isomerize to the more stable CH3OM(O)Cl molecules with the addition of the C-Cl bond of CH3Cl to one of the O=M bonds of MO2 upon annealing after broad-band light irradiation. The C-Cl activation by the MOx mechanism was interpreted by the calculated potential energy profiles.