Compared to modern fossil‐fuel‐based refineries, the emerging electrocatalytic refinery (e‐refinery) is a more sustainable and environmentally benign strategy to convert renewable feedstocks and energy sources into transportable fuels and value‐added chemicals. A crucial step in conducting e‐refinery processes is the development of appropriate reactions and optimal electrocatalysts for efficient cleavage and formation of chemical bonds. However, compared to well‐studied primary reactions (e.g., O₂ reduction, water splitting), the mechanistic aspects and materials design for emerging complex reactions are yet to be settled. To address this challenge, herein, we first present fundamentals of heterogeneous electrocatalysis and some primary reactions, and then implement these to establish the framework of e‐refinery by coupling in situ generated intermediates (integrated reactions) or products (tandem reactions). We also present a set of materials design principles and strategies to efficiently manipulate the reaction intermediates and pathways.