This paper demonstrates the feasibility of employing capillary electrophoresis (CE) to separate silver nanoparticles and nanocubes. We monitored the efficiency of these separations by obtaining electropherograms, employing a diode-array detection (DAD) system, as well as by analyzing scanning electron microscope (SEM) images of fractional collection of particles. Our results demonstrate not only the potential for separating silver nanoparticles and nanocubes by CE with DAD but also the ability to use such a technique to investigate the spectroscopic properties of silver nanoparticles having different shapes.