Electrochemical CO₂ reduction, with the energy input from renewable electricity, provides a green and alternative route for the generation of chemicals and fuels. However, its practice is currently challenged at two systematic levels: the lack of selective electrocatalysts to combat the strong competition from water reduction, and the lack of novel reactors for large-scale reaction rates and efficient product separation. In this talk, I will introduce the rational design of both catalytic materials and reactors towards practical CO₂ reduction performances. By dispersing transition metals into isolated single atoms with electronic structures significantly different from their bulk counterparts, we can dramatically suppress the competing hydrogen evolution and deliver an ultra-high CO₂ reduction selectivity of more than 95% under ambient conditions in water. Scaled-up synthesis and efficient reactors demonstrated the potential for practical applications. Furthermore, by designing a novel solid electrolyte reactor, we successfully demonstrated a continuous generation of pure liquid fuel solutions via CO₂ reduction. This technology eliminates the product separation process required in traditional CO₂ reduction electrolyzers, opening up its practical applications in the future.