The dual path mechanism for methanol decomposition on well-defined low Miller index platinum single crystal planes, Pt(111), Pt(110), and Pt(100), was studied using a combination of chronoamperometry, fast scan cyclic voltammetry, and theoretical methods. The main focus was on the electrode potential range when the adsorbed intermediate, COad, is stable. At such "CO stability" potentials, the decomposition proceeds through a pure dehydrogenation reaction, and the dual path mechanism is then independent of the electrodesubstrate surface structure. However, the threshold potential where the decomposition of methanol proceeds via parallel pathways, forming other than COad products, depends on the surface structure. This is rationalized theoretically. To gain insights into the controlling surface chemistry, density functional theory calculations for the energy of dehydrogenation were used to approximate the potential-dependent methanol dehydrogenation pathways over aqueous-solvated platinum interfaces.