Poly(vinyl pyrrolidone) was used successfully to control the size and distribution of silver nanoparticles generated on inorganic silica nanofibers. The inorganic nanofibers were electro spun using sol-gel chemistry of silicates, and the diameter of the prepared nanofibers was unaffected by adding up to 7% of poly(vinyl pyrrolidone). The silver ions, in the form of silver nitrate, were introduced into the silica nanofibers and reduced to metallic silver by ultraviolet irradiation with a subsequent thermal treatment. The size of the generated silver particles was decreased dramatically by adding poly(vinyl pyrrolidone). The size of the silver nanoparticles was 73 nm when no poly(vinyl pyrrolidone) was added but 23 nm with the addition of only 1% of poly(vinyl pyrrolidone). The extent of reduction could be checked by determining the concentration of silver ions leached into water from the silica nanofibers. After thermal treatment of the silica nanofibers, more than 99% of the silver remained in the nanofibers, indicating almost complete reduction of the silver ions to silver metal.