Polyhedral noble-metal nanocrystals have received much attention and wide applications as electrical and optical devices as well as catalysts. In this work, a straightforward and effective hydrothermal route for the controllable synthesis of the high-quality Pd-Ag alloy polyhedrons with uniform size is presented. The morphology, composition and structure of the Pd-Ag alloy polyhedrons are fully characterized by the various physical techniques, demonstrating the Pd-Ag alloy polyhedrons are highly alloying. The formation/growth mechanisms of the Pd-Ag alloy polyhedrons are explored and discussed based on the experimental observations and discussions. As a preliminary electrochemical application, the Pd-Ag alloy polyhedrons are applied in the formic acid oxidation reaction, which shows higher electrocatalytic activity and stability than commercially available Pd black due to the "synergistic effects" between Pd and Ag atoms.