The electrocatalytic properties of Bi, Sb and Pd decorated preferentially (100) oriented Pt thin films, denoted thereafter as Pt(100)(pref), for the oxidation of formic acid are investigated. Pt(100)(pref) - Bi and Pt (100)(pref) - Sb are prepared by spontaneous adsorption in Bi+3 and Sb+3 saturated solution, and the coverage is controlled by varying the adsorption time. In both cases, less than a monolayer is deposited. In contrast, the deposition of a monolayer of Pd on Pt(100)(pref) is achieved by underpotential deposition and galvanic exchange reaction with a pre-deposited monolayer of Cu. For short electrolysis period (t < 5 s), the activity of the electrode for the oxidation of formic acid follows the order Pt(100)(pref)-Pd ML > Pt (100)(pref)-Sb (theta = 75%) > Pt(100)(pref)-Bi (theta = 88%) > > Pt(100)(pref). However, after one hour of electrolysis, the Sb- and Bi-decorated Pt(100)(pref) electrode outperform both the Pd-decorated and the bare Pt(100)(pref) electrode (20, 15, 1 and 0.1 mAcm(-2) (geometric), respectively). (C) 2014 Elsevier Ltd. All rights reserved.