Conventional internal curing materials for high-performance cementitious system cannot easily have artificial modifications, such that the curing effect is difficult to control during the process. In this study, a novel microcapsule is proposed for controlled internal curing of cement-based materials. The microcapsules are synthesized by a double emulsion method to form a polymer shell-water core structure. The sensitivity of polymer shell to alkaline environments is used to trigger the release of core water. Thus, water release can be controlled by tailoring the shell thickness and microcapsules sizes by changing the polymer dosage and stirring rate during synthesis. The experimental results indicate that the novel microcapsules can effectively release water for internal curing of a cementitious matrix, which exhibits a high curing efficiency in terms of nearly autogenous shrinkage and increases the compressive strength. The novel microcapsules could be promising internal curing agents to enhance high-performance cement-based materials.