The activation and selectivity are the challenging problems always existing in the utilization of methanol as C-1 resource. Herein, a novel cobalt complex catalyzed process for preparation of methyl acrylate from methyl acetate and methanol at 50 degrees C-80 degrees C was firstly developed. Such cobalt complex stabilized with a PN5P-type pincer ligand, which can be easily prepared in gram scale, has high catalytic performance with the loading amount of only 5 mol.%. Systematic mechanism investigation revealed the cobalt complex activated by sodium methoxide via salt elimination could simultaneously interact with and catalyze the dehydrogenation of two-fold methanol into formaldehyde, followed by proceeding aldol condensation with methyl acetate in the presence of sodium methoxide. Besides the reaction atmosphere of O-2 was proved to be crucial for preventing the further hydrogenation of methyl acrylate into methyl propionate. Also, the mechanism-based kinetic model indicated the dehydrogenation of methanol was rate-controlling step with the activation energy of 89.0 +/- 1.1 kJ/mol.