Abstract Electrochemical C–C and C–N coupling reactions with the conversion of abundant and inexpensive small molecules, such as CO 2 and nitrogen‐containing species, are considered a promising route for increasing the value of CO 2 reduction products. The development of high‐performance catalysts is the key to the both electrocatalytic reactions. In this review, we present a systematic summary of the reaction systems for electrocatalytic CO 2 reduction, along with the coupling mechanisms of C–C and C–N bonds over outstanding electrocatalytic materials recently developed. The key intermediate species and reaction pathways related to the coupling as well as the catalyst‐structure relationship will be also discussed, aiming to provide insights and guidance for designing efficient CO 2 reduction systems.