In the last century, conventional strategies pursued to reduce or convert CO2have shown limitations and, consequently, have been pushing the development of innovative routes. Among them, great efforts have been made in the field of heterogeneous electrochemical CO2conversion, which boasts the use of mild operative conditions, compatibility with renewable energy sources, and high versatility from an industrial point of view. Indeed, since the pioneering studies of Hori and co-workers, a wide range of electrocatalysts have been designed. Starting from the performances achieved using traditional bulk metal electrodes, advanced nanostructured and multi-phase materials are currently being studied with the main goal of overcoming the high overpotentials usually required for the obtainment of reduction products in substantial amounts. This review reports the most relevant examples of metal-based, nanostructured electrocatalysts proposed in the literature during the last 40 years. Moreover, the benchmark materials are identified and the most promising strategies towards the selective conversion to high-added-value chemicals with superior productivities are highlighted.