Group 6 metal carbonyl complexes ([M(bpy)(CO())4], M = Cr, Mo, W) are potentially promising CO2 reduction electrocatalysts. However, catalytic activity onsets at prohibitively negative potentials and is highly dependent on the nature of the working electrode. Here we report in situ vibrational SFG (VSFG) measurements of the electrocatalyst [Mo(bpy)(CO)(4)] at platinum and gold electrodes. The greatly improved onset potential for electrocatalytic CO2 reduction gold electrodes is due to the formation of the catalytically active species [Mo(bpy)(CO)(3)]' via a second pathway at more positive potentials, likely avoiding the need for the generation of [Mo(bpy)(CO)(4)](2-). VSFG studies strength of the interaction between initially generated [Mo(bpy)(CO)(4)](.-) and the electrode is critical in enabling the formation of the active catalyst via the low energy pathway. By careful control of electrode material, solvent and electrolyte salt, it should therefore be possible to attain levels of activity with group 6 complexes equivalent to their much more widely studied group 7 analogues.