Taking the advantage of the inherent chemical activity arisen from the nitrogen incorporation for nitrogen-doped carbon nanotubes (NCNTs), we have developed a facile strategy for the construction of binary Pt–Ru/NCNT electrocatalysts. Alloyed Pt–Ru nanoparticles have been directly immobilized onto the outer surface of NCNTs without pre-modification due to the nitrogen participation. The Pt–Ru nanoparticles have a high dispersion, a narrow size distribution of 2.5–3.5nm and tunable chemical composition. These catalysts have been evaluated for methanol oxidation and show good stability and better CO tolerance than the monometallic Pt/NCNT catalyst due to the bifunctional and electronic effects. The Pt 5 Ru 5 /NCNT catalyst shows superior electrocatalytic performance to the commercial Pt 5 Ru 5 /C catalyst. The easy fabrication and excellent performance of the NCNT-based Pt–Ru alloy catalysts indicate their potential application in direct methanol fuel cells.