The electrocatalytic oxidation of methane proceed through two parallel reaction paths. The first path leads to CO formation, which can either poison the surface or subsequently oxidize to form CO 2. The second path leads to the formation of a CH xO intermediate that goes on to form CO 2 without ever forming CO. First-principle quantum chemical methods is used to probe the oxidation of methanol over model Pt surfaces. The presence of an aqueous media as well as constant electrochemical potential are necessary to appropriately model electrocatalytic systems. The primary reaction path for methanol occurred through the activation of the C-H bond to form the hydroxymethyl intermediate. Subsequent C-H and O-H activation steps led to CO, which poisons Pt. Methanol also reacts through a secondary path to form a surface methoxy intermediate, which subsequently goes on to form formaldehyde as a minor product. The results are consistent with overall experimental evidence. This is an abstract of a paper presented at the 229th ACS National Meeting (San Diego, CA 3/13-17/2005).