The catalytic decomposition of methyl formate into gaseous components in the presence of transition metal complexes, phosphine ligands, and water has been studied. It has been shown that in the presence of monometallic and bimetallic Rh/Ru catalysts, methyl formate can be converted to gas mixtures with high hydrogen content. These mixtures are suitable for use in hydroformylation, hydroaminomethylation, and hydroformylation-acetalization reactions; therefore, methyl formate may be thought of as being an alternative source of synthesis gas in oxo processes.