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Abstract Molecular catalysts for electrochemical CO₂reduction 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 CO₂by more than two electrons. In light of the recently discovered reactivity of heterogenized cobalt phthalocyanine molecules to catalyze CO₂reduction 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. The results show that the observed catalytic activities for both CO₂‐to‐CO and CO‐to‐methanol conversions in aqueous solutions of the cobalt phthalocyanines are predominantly heterogeneous in nature through the adsorbed species on the electrode.