The heterobimetallic ruthenium-cobalt catalytic system exhibited good catalytic performance and reusability in the reductive alkoxycarbonylation of olefins with carbon dioxide. Comparing to the previous system only consisting of ruthenium catalyst, binary catalyst system effectively reduced the usage of noble metal and ionic liquid additive. The respective contribution of ruthenium and cobalt catalysts in this multiple-step catalytic process was investigated by a series of condition-control experiments. The evolution of ruthenium catalyst and the occurrence of alkene hydrogenation during the reaction was explained by theortical calculation.