Electrocatalytic carbon dioxide (CO2) conversion into valuable chemicals paves the way for the realization of carbon recycling. Downsizing catalysts to single‐atom catalysts (SACs), dual‐atom catalysts (DACs), and sub‐nanocluster catalysts (SNCCs) has generated highly active and selective CO2 transformation into highly reduced products. This is due to the introduction of numerous active sites, highly unsaturated coordination environments, efficient atom utilization, and confinement effect compared to their nanoparticle counterparts. Herein, recent Cu‐based SACs are first reviewed and the newly emerged DACs and SNCCs expanding the catalysis of SACs to electrocatalytic CO2 reduction (CO2RR) to high‐value products are discussed. Tandem Cu‐based SAC–nanocatalysts (NCs) (SAC–NCs) are also discussed for the CO2RR to high‐value products. Then, the non‐Cu‐based SACs, DACs, SAC–NCs, and SNCCs and theoretical calculations of various transition‐metal catalysts for CO2RR to high‐value products are summarized. Compared to previous achievements of less‐reduced products, this review focuses on the double objective of achieving full CO2 reduction and increasing the selectivity and formation rate toward C–C coupled products with additional emphasis on the stability of the catalysts. Finally, through combined theoretical and experimental research, future outlooks are offered to further develop the CO2RR into high‐value products over isolated atoms and sub‐nanometal clusters.