The standard heterogeneous rate constants for the reduction of a series of viologen derivatives with a range of inter‐ring torsion angles were measured at Bi and Pt electrodes. The electrode potentials for the first one‐electron reduction of the viologens vary from −684 mV to −1070 mV vs. Ag/0.01 m Ag+; this enabled a comparison of the behaviour of metallic (Pt) and semi‐metallic (Bi) electrodes over a wide range of applied potentials. The differential capacitance (6.5 μF cm−2) of Bi/MeCN,TBAPF6 interfaces at the potential of zero charge (pzc=−0.60 V) is at least an order of magnitude greater than that calculated on the basis of the bulk Bi carrier density (3×1017 cm−3) and the differential capacitance (9.5 μF cm−2) of Pt/MeCN interfaces at their pzc (−0.43 V) is of the same order. The series of viologen derivatives exhibited simple one‐electron redox behaviour and showed similar rate constants at Pt (1.8×10−4–1.6×10−3 cm s−1) and Bi electrodes (1.1×10−4–1.9×10−3 cm s−1) after application of the Frumkin correction. These results demonstrate that the density of states at the Bi surface is much higher than in bulk. Finally, the Frumkin‐corrected standard rate constants were observed to be inversely correlated with the inter‐ring torsion angle of the viologens.