We demonstrate a simple wet-chemical route for the high-yield synthesis of flowerlike silver nanostructures consisting of single crystalline Ag nanoplates by mixing AgNO3 and p-phenylenediamine (PPD) in the presence of polyvinylpyrrolidone (PVP) at room temperature. PPD serves both as a reducing agent, and as an architecture soft template with PVP to the formation of such Ag nanostructures. It is found that the presence of PVP has a significant effect on the formation and growth of these novel nanostructures. The flowerlike silver nanostructures could serve as highly sensitive and reproductive surface-enhanced Raman scattering (SERS) substrates for chemical and biological detection.