Ethylene glycol (EG) has been widely utilized to fabricate silver nanoparticles with uniform size and morphology. However, the majority of the work reported to date using EG routinely require not only heating, but also a surfactant. In the present paper, we report a surfactant-free and facile method for the synthesis of fairly monodisperse smaller silver nanoparticles (~6 nm) through the reaction of silver ions with EG by using tungstates (such as potassium tungstate, sodium tungstate) as catalysts at room temperature. Particularly, in this method, tungstates as catalysts can dramatically speed up the reduction of silver ions, and EG acts as both a solvent and a reducing agent to reduce silver ions to Ag metal. Meantime, we have carried out a series of experiments to investigate the performance of the as-prepared silver nanoparticles. It was found that the silver nanoparticles show excellent catalytic activity for the reduction of 4-nitrophenol in the presence of NaBH4.