A PtCo catalyst was synthesized by using a specific colloidal preparation route and a carbothermal reduction at 800°C. This treatment, caused the occurrence of a primitive cubic ordered (L1₂) phase, and a mean crystallite size of 3.3 nm, as well as a suitable degree of alloying. The electrocatalyst was subjected to the pre-leaching procedure to modulate the surface characteristics. The catalyst after the carbothermal reduction at 800°C was further investigated at the cathode of a direct methanol fuel cell (DMFC). A comparison with a commercial Pt catalyst was carried out. A higher performance in DMFC was obtained by using the bimetallic PtCo catalyst.