We report here a facile PVP-assisted chemical reduction process for preparation of various palladium (Pd) nanocrystals including nanoplates, octahedrons, porous nanocrystals, and hollow nanocrystals. The synthesis involved only the use of PdCl2 as the precursor, PVP as the reducing and stabilizing agents, and a specific salt like NaCl or NH4OH as the additive. By modulating the relevant reaction conditions such as the amount of PdCl2, the amount of additive, and the reaction temperature, we were able to obtain anisotropic Pd nanocrystals with controllable morphologies. As compared to the commercial Pd nanoparticles, the four types of Pd anisotropic nanocrystals all exhibited superior electrocatalytic activities toward hydrogen adsorption/desorption, revealing their catalytic potential in relevant electrochemical reactions. Furthermore, among the four Pd samples, hollow nanocrystals possess the highest current density of formic acid oxidation and the largest If/Ib ratio, demonstrating that they could be promisingly used as highly-efficient CO-resistant electrocatalyst in the direct formic acid fuel cell.