Electrochemical reduction of carbon dioxide (CO₂) presents a compelling strategy for mitigating greenhouse gas emissions while simultaneously producing valuable chemical feedstocks. Transitioning from conventional precious metal-based catalysts to carbon-supported macrocyclic complexes offers a significant opportunity to reduce costs and enhance the economic viability of this technology. This talk introduces a systematic molecular engineering approach to optimize cobalt phthalocyanine (CoPc) catalysts for improved CO₂ electroreduction performance. By employing covalent ligation, polymerization, and strategic substitution of peripheral groups, we fine-tune the electronic structure, active site accessibility, and stability of CoPc complexes. These targeted modifications yield substantial enhancements in catalytic activity, selectivity, and operational durability under ambient conditions. In situ spectroscopic techniques and variable-frequency square wave voltammetry elucidate the structure–function relationships that underpin catalytic behaviour. Our findings establish a versatile framework for the rational design of cost-effective, high-performance molecular catalysts, advancing the development of scalable carbon capture and conversion technologies.