Abstract: The performances of humidity diffusion and shrinkage of cement-based materials are important aspects of the durability of concrete. The effects of highly crosslinked resin emulsion on shrinkage and the humidity diffusion of cement-based materials were studied. Two monomers octyl trimethoxy silane and propyl trimethoxy silane were made into highly crosslinked resin emulsion via emulsion polymerization synthesis method. The results showed that the amount of water loss of cement-based materials increased with the decrease of relative humidity. Silicone resin emulsion prevents the hydration process of cement-based materials, which controlled the early shrinkage of the cement-based materials effectively, so that the shrinkage of mortar test block with silicone resin emulsion is smaller than that of untreated mortar. With the increase of the silicon resin emulsion admixture, mortar initial shrinkage reduced, meanwhile, the longer specimen drying, the smaller the dry shrinkage of the silicone emulsion.