The mechanism of electrochemical reduction of acetophenone in 1-butyl-3-methylimidazolium tetrafluroborate ([BMIM][BF(4)]) under nitrogen (N(2)) and carbon dioxide (CO(2)) atmospheres have been investigated using transient voltammetry, steady-state voltammetry, bulk electrolysis and numerical simulation. Under a N(2) atmosphere, acetophenone undergoes a one-electron reduction to the radical anion followed by rapid dimerization reactions with an apparent rate constant of 1.0 x 10(6) M(-1) s(-1). In contrast, under a CO(2) atmosphere, the electrochemical reduction of acetophenone is an overall two-electron transfer chemically irreversible process with the final electrolysis product being 1-phenylethanol, instead of the anticipated 2-hydroxy-2-phenylpropionic acid resulting from an electrocarboxylation reaction. A proton coupled electron transfer pathway leading to the formation of 1-phenylethanol requires the presence of a sufficiently strong proton donor which is not available in neat [BMIM][BF(4)]. However, the presence of CO(2) enhances the C-2 hydrogen donating ability of [BMIM](+) due to strong complex formation between the deprotonated form of [BMIM](+), N-heterocyclic carbene, and CO(2), resulting in a thermodynamically favorable proton coupled electron transfer pathway.