Serving as shape control agent, polyvinyl pyrrolidone (PVP) has been widely used in chemical synthesis of metal nanoparticles. However, the role of molecular weight (MW) of PVP has been rarely concerned. In this study, we show a facile method to control the shapes of silver nanocrystals using PVP with different MWs. PVPMW=8,000, PVPMW=29,000, PVPMW=40,000, and PVPMW=1,300,000 are compared in the present study. Surprisingly, high-yield silver rodlike nanostructures, nanospheres, and nanowires can be obtained under the same growth environment and reactant concentrations by simply changing the MW of PVP. The mechanism studies of the role of PVP with different MWs in the growth process were carried out systemically using the morphology and spectroscopic measurement, FT-IR spectrum analysis, and seed crystallization monitoring. The results indicate that the MW of PVP plays a determinant role in the morphology and optical property control of the silver nanocrystals. Meantime, the concentration of PVP was found to be an assistant factor to further improve the shape and the yield of the synthesized nanocrystals.