The effect of the chain length of polyvinyl pyrrolidone (PVP) on the structures of silver nanowires (AgNWs) is explored in this study. It was found in the experiments that PVP, when serving as a capping agent, has a great impact on the morphology and structure of AgNWs. By means of a series of experiments and the inquiry of the growth mechanism, the critical minimum PVP chain length for the successful formation of uniform nanowires was discovered, below which only nanoparticles or short nanorods can be obtained. Surprisingly, a core–shell structure of a nanowire with a polycrystal was observed when PVP with a very long chain length was employed in the processing.