Pt-Pd bimetallic alloy nanostructures with highly selective morphologies such as cube, bar, flower, concave cube, and dendrite have been achieved through a facile one-pot solvothermal synthesis. The effects of shape-controllers (sodium dodecyl sulfate (SDS), ethylenediamine-tetraacetic acid disodium salt (EDTA-2Na), NaI) and solvents (water/DMF) on the morphologies were systematically investigated. The electrocatalytic activities of these Pt-Pd alloy nanostructures toward formic acid oxidation were tested. The results indicated that these alloy nanocrystals exhibited enhanced and shape-dependent electrocatalytic activity toward formic acid oxidation compared to commercial Pt black and Pt/C catalysts.