Novel Pd flower-like nanostructured networks are synthesized via a simple CO-assisted reduction. The morphology and size of the Pd nanostructures are found to strongly depend on the temperature and solvent during the synthesis process. Such Pd flower-like nanostructured networks exhibit a much enhanced activity of about 3 times of that on conventional Pd nanoparticles towards the electrocatalytic oxidation of formic acid. The specific activity of formic acid oxidation on Pd nanostructures is also greatly improved, indicating that the formation of flower-like nanostructured networks is beneficial for the electrooxidation of formic acid. Thus, it could be served as highly active catalyst for formic acid electrooxidation although the stability needs to be greatly improved. (C) 2014 Elsevier B.V. All rights reserved.