The reductive electrochemistry of substituted benzophenones in [Bmpy][NTf2] and [Bmim][NTf2] ionic liquids is presented where electrochemistry in [Bmpy] medium results in reversible formation of the radical anion and the dianion species indicating that neither protonation nor ion pairing occurs; whereas in [Bmim], its protic nature results in radical anion protonation leading to an ECE or a DISP1 post electron transfer process and thus irreversibility. The mediated oxidation of alcohols by TEMPO is also presented along with a mechanism / kinetic model involving a rate-controlling pre-equilibrium process which generated the electroactive alcoholate species. The ability of electrochemistry to inform us about the physiochemical nature of ionic liquids, as well as ionic liquids' ability to facilitate and enable electrochemistry, is also discussed.