In this study, a novel phase-change microcapsule with hybrid shell was prepared via a “two-step” reaction in an emulsion system. In the process, methacryloxy propyl trimethoxyl silane and methyl methacrylate were used as a precursor shell material and octadecane as the core material. Scanning electron microscope, thermogravimetric analyzer, differential scanning calorimetry and energy dispersive X-ray spectroscopy were employed to characterize the morphology, latent heat property and component of the shell of microcapsules, respectively. The results showed that the shell of microcapsules was composed of silicon and P(MMA-co-DVB), with the core material content of the microcapsules over 80%, and the size of microcapsules could be controlled by varying the content of the surfactant.