The oxygen reduction activity and methanol tolerance of Pt–Bi/C electrocatalysts were studied using electrochemical voltammetric techniques including rotating ring-disk electrode. The Pt–Bi/C catalyst was prepared via a polyol method and subjected to heat treatment to increase the degree of alloying. X-ray diffraction studies revealed the unalloyed character of the as-prepared catalyst and alloy formation upon heat treatment. The electrochemical behaviour of both catalysts showed different behaviour in dilute acid electrolytes, namely sulphuric and perchloric acids. In both electrolytes, the oxygen reduction reaction was found to occur via the four-electron process revealing that the mechanism of oxygen reduction is unaltered even in the presence of excess of methanol. Pt–Bi/C catalyst material showed dramatically different properties and reactivity with respect to oxygen reduction activity and methanol tolerance in perchloric and sulphuric acids. The onset potential for oxygen reduction reaction (ORR) significantly shifted by about 100 mV to more negative values and at the same time the current density was significantly enhanced. This type of non-ideal methanol-tolerant behaviour among Pt bimetallics and a “trade off” is common with all the known so-called methanol tolerant combinations of Pt. In general, the Pt–Bi surface appeared to have a negligibly lesser sensitivity towards methanol activity compared to pure platinum.