Single-crystal cubes and tetrahedrons of silver with truncated corners/edges have been prepared for the first time in high yields by reducing silver nitrate with ethylene glycol heated to 148 °C in the presence of poly(vinyl pyrrolidone) and a trace amount of sodium chloride. These nanoparticles were relatively monodisperse in size and shape, and their dimensions could be readily controlled in the range of 20 to 80 nm by varying the reaction time and other experimental parameters. We propose that the defects inherent in twinned nuclei of silver led to their selective etching and dissolution by chloride and oxygen (from air), leaving only the single crystalline ones to grow into nanoscale cubes and tetrahedrons.