Periodic DFT calculations have been performed to systematically investigate the mechanisms of methanol decomposition and oxidation on the PtRu/Pt(111) surface. Geometries and energies for the primary species involved are analyzed and the reaction network has been mapped out. The calculation shows that among three initial CH, OH, and CO bond scissions of methanol, the OH bond scission is found to be the most favorable and bears a lower energy barrier than the desorption of methanol. The decomposition of CH3O occurs via the path CH3O→CH2O→CHO→CO with the limiting step of the first dehydrogenation. Although the oxidation of CO is hindered by a high barrier, the CHO oxidation to CHOOH could occur facilely. Further decomposition of formic acid to CO2 and/or CO could occur via four possible pathways, that is, initial CH, OH, and CO bond activations as well as simultaneous activation of CH and CO bonds, where the first pathway, HCOOH→COOH→CO2, is the most favorable from a kinetic point of view. Compared to that on Pt(111), methanol on PtRu/Pt(111) prefers to decomposition rather than desorption and then oxidation via the favorable non-CO path with a lower rate-determining energy barrier of CH3O→CH2O for the whole reaction, which indicates that PtRu alloy can improved tolerance toward CO poisoning compared with pure Pt.