Selective aerobic oxidation of benzyl alcohol to benzaldehyde by a (bpy)CuI(IM)/TEMPO catalyst (IM represents differently substituted imidazoles) has been studied by simultaneous operando electron paramagnetic resonance/UV-vis/attentuated total reflectance infrared spectroscopy in combination with cyclic voltammetry to explore the particular role of imidazole in terms of ligand and/or base as well as of its substitution pattern on the catalytic performance. For molar ratios of IM/Cu ≥ 2, a (bpy)CuI/II(IM)a(IM)b complex is formed, in which the Cu-N distances and/or angles for the two IM ligands a and b are different. The coordination of a second IM molecule boosts the oxidation of CuI to CuII and, thus, helps to activate O2 by electron transfer from CuI to O2. The rates of CuI oxidation and CuII reduction and, thus, the rates of benzaldehyde formation depend on R of the R-N moiety in the IM ligand. Oxidation is fastest for R = H and alkyl, while reduction is slowest for R = H. The CuI/CuII interplay leads to decreasing total benzaldehyde formation rates in the order R (I+ effect) > R (conjugated system) > R = H.