The reactions of (1) CH4 + MgO → MgOH• + CH3• and (2) CH4 + MgO → Mg + CH3OH have been studied on the singlet spin state potential energy surface at the MP2/6-311+G(2d,2p) level. These two reaction channels, both involving intermediates and transition states, have been rationalized by the structures of the species involved, natural bond orbital (NBO), and vibrational frequency analysis. We have considered two initial interacting models between CH4 and MgO: a collinear C-H approach to the O end of the MgO forming the MgOCH4 complex with C3V symmetry and three hydrogen atoms of the methane point to the Mg end of the MgO forming the OMgCH4 complex with C1 symmetry. The calculations predict that reactions 1 and 2 are exothermic by 39.8 and 86.5kJmol-1, respectively. Also, the former reaction proceeds more easily than the latter, and the complex HOMgCH3 is energetically preferred in the reaction of MgO + CH4.