Molecular catalysts for electrochemical CO2 reduction have traditionally been studied in their dissolved states. However, the heterogenization of molecular catalysts has the potential to deliver much higher reaction rates and enable the reduction of CO2 by more than two electrons. In light of the recently discovered reactivity of heterogenized cobalt phthalocyanine molecules to catalyze CO2 reduction into methanol, direct comparison is needed to uncover the distinct catalytic activity and selectivity in homogeneous catalysis versus heterogeneous catalysis. Herein, soluble cobalt phthalocyanine derivatives were synthesized, and their catalytic activities in the homogeneous solutions were evaluated.