The underpotential deposition (UPD) shifts of different metallic couples in acetonitrile and propylene carbonate are estimated using work function differences, lattice coordination numbers, and adsorption energies of solvent dipoles. The bulk deposition arising from monolayer and multilayer formation is considered. A satisfactory agreement of the UPD shift with the experimental data deduced from anodic stripping voltammetry is noticed. Apart from evaluating the surface potential of electrons in metals using the potential of monolayer adsorption and bulk deposition, the significance of the methodology in the development of electrochemical capacitors is indicated.