The reactions of tantalum monoxide (TaO) and dioxide (TaO(2)) molecules with methanol in solid neon were investigated by infrared absorption spectroscopy. The ground-state TaO molecule reacted with CH(3)OH in forming the CH(3)OTa(O)H molecule via the hydroxylic hydrogen atom transfer from methanol to the metal center spontaneously on annealing. The observation of the spontaneous reaction is consistent with theoretical predictions that the OH bond activation process is both thermodynamically exothermic and kinetically facile. In contrast, the TaO(2) molecule reacted with CH(3)OH to give primarily the TaO(2)(CH(3)OH) complex, which further rearranged to the CH(3)OTa(O)OH isomer via the hydroxylic hydrogen atom transfer from methanol to one of oxygen atom of metal dioxide upon visible light excitation.