Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core[poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and thecomplex effect of crown ether with Ag+ and Ag. The size of silver nanoparticles could be tailored by controllingthe initial concentrations of the polymer and Ag+, and the molecular weight of the polymer. The emissionof silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticlesstabilized by the polymer was significantly increased due to the complex effect between the crown etherembedded in the polymer and the silver nanoparticles.