Formic acid oxidation was studied on platinum-bismuth deposits on glassy carbon (GC) substrate. The catalysts of equimolar ratio were prepared by potentiostatic deposition using chronocoulometry. Bimetallic structures obtained by two-step process, comprising deposition of Bi followed by deposition of Pt, were characterized by AFM spectroscopy which indicated that Pt crystallizes preferentially onto previously formed Bi particles. The issue of Bi leaching (dissolution) from PtBi catalysts, and their catalytic effect alongside the HCOOH oxidation is rather unresolved. In order to control Bi dissolution, deposits were subjected to electrochemical oxidation, in the relevant potential range and supporting electrolyte, prior to use as catalysts for HCOOH oxidation. Anodic striping charges indicated that along oxidation procedure most of deposited Bi was oxidized. ICP mass spectroscopy analysis of the electrolyte after this electrochemical treatment revealed that Bi was only partly dissolved indicating the possibility for formation of some Bi oxide species. Moreover, EDX analysis of the as prepared (Pt@Bi/GC) catalysts and those oxidized confirmed appreciably higher content of oxygen in the latter. Catalysts prepared in this way exhibit about 10 times higher activity for formic acid oxidation in comparison to pure Pt, as revealed both by potentiodynamic and quasy-potentiostatic measurements. This high activity is the result of well-balanced ensemble effect induced by Bi-oxide species interrupting Pt domains. Prolonged cycling and chronoamperometry tests disclosed exceptional stability of the catalyst during formic acid oxidation. The activity is compatible with the activity of previously studied Pt2Bi alloy but the stability is significantly better. (C) 2014 The Electrochemical Society. All rights reserved.