A modified silver electrode was prepared by the self-assembly of a thiol-derivatized neoglycoconjugate, forming a 2D surface with maltose functionality. This self-assembled-monolayer-modified electrode was utilized for adsorption and spectroelectrochemical studies of tetraheme-containing type II cytochrome c3. The glycosylated surface allowed for the determination of the hemes' redox potentials and demonstrated enhanced spectroelectrochemical performance, in comparison to the widely used self-assembled monolayer of 11-mercapto-undecanoic acid.