Additives with different structures and properties were selected to prepare the silver powder under the same experimental conditions. The effect of the different additives on the morphology and particle diameter of the silver powder was compared and analyzed. The results show that, using the no branched or less branched long-chain polymer compound as additive is more helpful to prepare the silver powder with smooth surface and spherical shape. In this paper, based on the additive of PVP K30, the silver powder with excellent dispersion, spherical shape and good crystallization was prepared successfully by adjusting and optimizing the experimental parameters. The particle size is about 2.5 ~ 3 μm and the tap density is 4.2 g/cm3, which can meet the required index of silver powder used for the solar electronic paste.