The reaction between silver nitrate and poly(N-vinyl-2-pyrrolidone) (PVP) in pyridine at ambient conditions could lead to the formation of spherical nanoparticles or quadrilateral and triangular silver nanoplates, depending on the silver-to-PVP ratio used. It is proposed that the spherical Ag nanoparticles, which were formed early in the reaction, were transformed into nanoplates through an Ostwald ripening process driven by the bridging flocculation of small spherical Ag nanoparticles. This unique and hitherto unreported shape evolution process was carefully followed by a combination of techniques, viz., UV-visible spectroscopy, TEM, and powder X-ray diffraction.