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Elemental doping is an effective approach to modify the local electronic structure of active sites. Herein, we tailored tin electrocatalysts with boron doping to tune and stabilize the valence state of Sn. The initial screening in the flow cell with 1 M KOH showed that the boron-doped Sn (Sn (B)) exhibited both higher formate production efficiency and rate than the pristine Sn particles in CO 2 electroreduction. The optimal Sn (B) catalyst was translated to a solid-state electrolyzer incorporating solid electrolyte (either H+ or OH− solid conductor). The H+ solid conductor enabled direct production of formic acid, however, it sacrificed the anodic energy efficiency compared to formate production in the OH− solid conductor. H+ conductor cell produced a Faradic efficiency for formic acid of 88% with energy efficiency of 41% at cell voltage of 3.0 V and partial current density of 60.3 mA cm− 2. Whereas, the Faradic efficiency of …