The high purity silver was leaching-out and prepared using a nitric acid dissolution method from waste photosensitive film. The grain size controllable spherical ultrafine silver was prepared with ascorbic acid as reducing agent, macromolecules (PVP) and surfactant (TEA) as dispersant. The results show that the leaching effect is good, and high-purity 99.5% silver of higher content can be obtained when the concentration of nitric acid is 1.6 mol·L-1, the leaching temperature is 50 oC, and the leaching is 10 min and 3 times. Superfine silver powder of uniform size 0.15 μm, regular shape and good dispersion can be prepared when the reaction temperature is 20 oC, pH value of silver nitrate solution is 8, the concentration of silver nitrate is 0.02 mol·L-1, the m(PVP)/m(AgNO3)>4.5 and m(TEA)/m(AgNO3)=1