Electroreduction of small molecules such as CO₂, N₂, and NO₃⁻ is one of the promising routes to produce sustainable chemicals and fuels and store renewable energy, which could contribute to our carbon neutrality goal. Emerging multicomponent electrocatalysts, integrating the advantages of individual components of catalysts, are of great importance to achieve efficient electroreduction of small molecules via activation of inert bonds and multistep transformation. In this review, some basic issues in the electroreduction of small molecules including CO₂, N₂, and NO₃⁻ are briefly introduced. We then discuss our fundamental understanding of the rule of interaction in multicomponent electrocatalysts, and summarize three models for multicomponent catalysts, including type I, “a non-catalytically active component can activate or protect another catalytic component”; type II, “all catalytic components provide active intermediates for electrochemical conversion”; and type III, “one component provides the substrate for the other through conversion or adsorption”. Additionally, an outlook was considered to highlight the future directions of multicomponent electrocatalysts toward industrial applications.