PtRu and PtRuW ternary electrocatalysts were synthesized using an NaBH4 reduction method. A uniform distribution of particles, with average particle size of 3-3.5 nm was indentified from X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemically active surface area was slightly decreased after the addition of W into PtRu. When W was added to PtRu, the specific and mass activity of methanol electro-oxidation was increased. The most active catalyst was Pt5Ru4W, of which specific and mass activities were 265.38 mA/m2 and 6.21 A/g.catal, respectively. The specific and mass activity was 390 and 320% higher than that of PtRu.