In this study, polyvinylpyrrolidone (PVP) was introduced into an Ag deposition-based electrochromic (EC) device as a capping agent for electrodeposited Ag nanoparticles (AgNPs) to improve the coloration characteristics of EC devices and to precisely control the size and shape of the AgNPs. Through the coordination of PVP molecules with Ag+ ions in the EC electrolyte, the critical voltage for the deposition of AgNPs decreased, resulting in a lower operating voltage of the EC device in comparison with the conventional one. Because particle growth and AgNP aggregation were suppressed by the capping effect of PVP, uniform electrodeposition of AgNPs was achieved. Aggregation suppression enabled vivid cyan, yellow, and red coloration using a simple driving procedure. The suppression of AgNP aggregation by PVP was demonstrated even in an electrochemical system. Furthermore, the capping effect of PVP also improved image retention. Better color retention properties were achieved even without the use of any counter-modified electrode cells.