Precise electrochemical synthesis of commodity chemicals and fuels from CO ₂ building blocks provides a promising route to close the anthropogenic carbon cycle, in which renewable but intermittent electricity could be stored within the greenhouse gas molecules. Here, we report state-of-the-art CO ₂ -to-HCOOH valorization performance over a multiscale optimized Cu–Bi cathodic architecture, delivering a formate Faradaic efficiency exceeding 95% within an aqueous electrolyzer, a C-basis HCOOH purity above 99.8% within a solid-state electrolyzer operated at 100 mA cm ⁻² for 200 h and an energy efficiency of 39.2%, as well as a tunable aqueous HCOOH concentration ranging from 2.7 to 92.1 wt%. Via a combined two-dimensional reaction phase diagram and finite element analysis, we highlight the role of local geometries of Cu and Bi in branching the adsorption strength for key intermediates like *COOH and *OCHO for CO ₂ reduction, while the crystal orbital Hamiltonian population analysis rationalizes the vital contribution from moderate binding strength of η ² (O,O)-OCHO on Cu-doped Bi surface in promoting HCOOH electrosynthesis. The findings of this study not only shed light on the tuning knobs for precise CO ₂ valorization, but also provide a different research paradigm for advancing the activity and selectivity optimization in a broad range of electrosynthetic systems.

A remarkable advance in BiFeO ₃ -based photocathodes was achieved by introducing a functional charge collection layer to boost the charge carrier dynamics by reducing the charge transport barrier and prolonging the lifetime of photocarriers.