A dicationic Re bipyridine-type complex, fac-Re(6,6'-(2-((trimethylammonio)-methyl)phenyl)-2,2'-bipyridine )(CO)3Cl hexafluorophosphate (12+), has been synthesized, and its electrochemical behavior under Ar and CO2 has been investigated. The presence of pendent tetra-alkylammonium cations induces an anodic shift in the electrocatalytic potential for CO2 reduction relative to structurally similar model complexes. The electrochemical mechanisms in anhydrous CH3CN and in the presence of weak acids (water or trifluoroethanol) have been analyzed using cyclic voltammetry assisted by infrared spectroelectrochemistry and theoretical calculations. The dication enables catalysis at a diminished potential through Coulombic stabilization of the doubly reduced pentacoordinate species, its CO2 adduct, the hydroxide anion, and the conjugate base formed during acid-assisted C-OH bond cleavage of the metallocarboxylic acid to the metallocarbonyl and H2O. The major reduction product is CO, but in the presence of trifluoroethanol, formate is also produced with 14% Faradaic efficiency.