Abstract: Solid materials Li₃PO₄, FePO₄ and 5% Li₃PO₄·FePO₄ were prepared by a method of precipitation. The behavior of laser stimulated oxidative coupling of methanol to ethandiol on these materials have been studied by XRD, IR, TPD techniques and laser stimulated surface reaction(LSSR). The results showed that there are two kinds of methanol adsorption on the solid surfaces: molecular adsorption of C-H site of CH₃OH on P=O bonds of catalysts and dissociation adsorption of CH₂OH radicals on Lewis acid sites of metal. The adsorption types were depended on the interaction between Li₃PO₄ and FePO₄. Selective excitation of the surface P=O bonds by 1077 cm^-1 laser photon caused the activation of surface lattice oxygen,which on reacting with adsorbed CH₃OH and dehydrogenating it to CH₂OH led to oxidative coupling of CH₂OH to ethandiol on Lewis acid sites. Increase of the reaction temperature had the effects of replenishing the energy density of laser photon and promoting the desorption of the products. It also caused thermal reactions with formation of by products, e.g. dimethyl ether, formaldehyde and ethylene.