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Abstract A series of molecular Mn catalysts featuring aniline groups in the second‐coordination sphere has been developed for electrochemical and photochemical CO₂reduction. The arylamine moieties were installed at the 6 position of 2,2’‐bipyridine (bpy) to generate a family of isomers in which the primary amine is located at theortho‐(1‐Mn),meta‐(2‐Mn), orpara‐site (3‐Mn) of the aniline ring. The proximity of the second‐sphere functionality to the active site is a critical factor in determining catalytic performance. Catalyst1‐Mn, possessing the shortest distance between the amine and the active site, significantly outperformed the rest of the series and exhibited a 9‐fold improvement in turnover frequency relative to parent catalyst Mn(bpy)(CO)₃Br (901 vs. 102 s⁻¹, respectively) at 150 mV lower overpotential. The electrocatalysts operated with high faradaic efficiencies (≥70 %) for CO evolution using trifluoroethanol as a proton source. Notably, under photocatalytic conditions, a concentration‐dependent shift in product selectivity from CO (at high [catalyst]) to HCO₂H (at low [catalyst]) was observed with turnover numbers up to 4760 for formic acid and high selectivities for reduced carbon products.