A series of rhenium(I) fac-tricarbonyl complexes containing pendent arylamine functionality in the second coordination sphere have been developed and studied as electrocatalysts for carbon dioxide (CO2) reduction. Aniline moieties were appended at the 6 position of a 2,2'-bipyridine (bpy) donor in which the primary amine was positioned at the ortho- (1-Re), meta- (2-Re), and para- (3-Re) sites of the aniline substituent to generate a family of isomers. The relationship between the catalyst structure and activity was explored across the series, and the catalytic performance was compared to that of the benchmark catalyst Re(bpy)(CO)(3)Cl (ReBpy). Catalysts 1-Re, 2-Re, and 3-Re outperform the benchmark catalyst both in anhydrous acetonitrile and with added trifluoroethanol (TFE) as an external proton source. In the presence of TFE, the aniline-substituted catalysts convert CO2 to carbon monoxide (CO) with high Faradaic efficiencies (>= 89%) and have superior turnover frequencies (TOFs) relative to ReBpy (72.9 s(-1)), with 2-Re having the highest TOF of the series at 239 s(-1), a value that is twice that of the next most active catalyst. TOFs of 123 and 109 s(-1) were observed for the ortho- and para-substituted aniline complexes (1-Re and 3-Re), respectively. Indeed, catalytic activities vary widely across the series, showing a high sensitivity to the position of the amine functionality relative to the rhenium active site. IR and UV-vis spectroelectrochemical experiments were conducted on the aniline-substituted systems, revealing important differences between the catalysts and mechanistic insight.