Using simple and efficient template method, sphere assembled structure; shuttle-like structure and flake assembled structure of calcium carbonate were obtained. The morphologies of products were researched, and the sphere assembled calcium carbonate with large surface was modified and combined with silver nanoparticles to obtain the silver nanoparticle/calcium carbonate composite for the first time. The composite has extensive applications in sterilization and medicine areas etc. The composite can not only reduce the silver quantity, but also provide a good route for applications of calcium carbonate nanomaterials