Additives with different structures and properties were selected to prepare silver powder under the same experimental conditions. The effect of different additives on the morphology and particle size of the silver powder was analyzed. The results show that the silver powder with smooth surface and spherical shape is obtained more easily when using long-chain polymer compounds with no or less branches as the additive. The silver powder with excellent dispersion, spherical shape and good crystallization is prepared successfully with PVP K.30 as the additive, by optimizing experimental parameters. The particle size is 2.5~3 μm and the tap density is 4.2 g/cm~3, which can meet the requirement of silver powder used for solar electronic paste.