The sequential two-electron reduction of benzaldehyde to the radical anion and dianion species in 1-butyl-3-methylimidazolium triflimide and 1-butyl-1-methylpyrrolidinium triflimide is reported. In 1-butyl-1-methylpyrrolidinium triflimide, the heterogeneous electrochemistry and follow-up chemical reactivity are essentially equivalent to that in conventional molecular-solvent-based electrolytes where no interaction with the media is observed. In 1-butyl-3-methylimmidazolium triflimide, reduction occurs via the same two heterogeneous processes; however, the apparent heterogeneous rate constants are smaller by ca. 1 order of magnitude which leads to quasi-reversible electrochemical behavior. Since the bulk viscosities of the liquids are similar, the slower heterogeneous kinetics are attributed to local interfacial viscosity due to local ordering in the imidazolium-based medium. Also, a dramatic anodic shift in the reduction potentials is observed in 1-butyl-3-methylimidazolium triflimide media that is attributed to a stabilizing interaction of the radical anion and dianion species with the imidazolium cation.