A nanoparticle synthesis for naked PtRu, PtMo, PtW, and PtNi alloys of average 1.7 nm is reported. New nanoparticles in this method were examined in the anode electrocatalysis for direct methanol fuel cells (DMFCs). The high activity of Pt alloy electrocatalysts for methanol oxidation was rationalized by the proper alloy formation and surface chemical composition of nanoparticles to satisfy bifunctional and electronic effects, as evidenced by transmission electron microscopy (and energy-dispersive X-ray), X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical methods. The small-sized nanoparticles showed the possibility to help the enhancement of the DMFC unit cell performance.