Hydrogenation of CO2 promoted by heterogeneous metal catalysts has found commercial applications. Furthermore, homogeneous catalysts based on transition metal complexes have also been demonstrated to be useful in the CO2 conversion to formate under relatively mild reaction conditions. In the course of our study aimed to uncover the availability of copper complexes, we focused on the ligand acceleration effect on the hydrogenation reaction. Improved formate yield and catalytic activity were obtained by adding selected bisoxazoline ligands to a copper catalyst system. The results presented here open up the possibility to develop efficient copper catalysts based on appropriate ligand design.