Alkyl formates can be formed from CO2-containing syngas with C-1-C-4 alkyl alcohol solvents in the presence of potassium carbonate, which changed to potassium formate as catalyst. The formates can be in situ hydrogenoly sized further to produce methanol effectively over manganese oxide or magnesia-supported copper catalysts. These homogeneous and heterogeneous catalysts constitute a novel system for methanol synthesis from CO/CO2/H-2 even at 443 K.