High surface area Pt, Pd, and Pt/Pd catalyst structures were prepared by electrodeposition at large overpotentials, as well as through spontaneous deposition of Pd on pure Pt structures. The resulting structures provide high surface area electrocatalysts on microfabricated silicon substrates via MEMS compatible preparation methods. The activity of these catalyst structures for formic acid oxidation was studied using electrochemical techniques, and improved activity toward formic acid oxidation was observed as a result of increased surface areas and/or different chemical composition of the catalyst structures. Catalyst structures with dendritic as well as other high surface area morphologies exhibited increased activity for formic acid electro-oxidation due to their larger number of active sites. Similarly, Pd-containing catalysts were found to be significantly more active than the pure Pt catalyst structures. In chronoamperometry at low anode potentials (which corresponds to high cell potentials in a fuel cell), Pt structures modified by spontaneously deposited Pd (Pt/Pd-SD) were found to be the most active electrocatalysts, while pure Pd structures showed higher activity at higher anode potentials, i.e. at lower cell potentials. Pure Pd catalyst structures may thus be a good choice for fuel cells continuously operating under high load.