MnO 2 particles were prepared by a hydrothermal method and characterized via the SEM imaging, XRD and FTIR analyses, showing that the individual particles were spherical and less than 1.0 μm in diameter but were clustered in α type crystal. The particles were then added into the n-octadecane to form a new class of phase-change energy storage composites. After that, the composite powder was wrapped into polyethylene by the suspension polymerization, forming microcapsules with an average size 4.9–5.6 μm in diameter. Eventually the morphology and thermal properties of the microcapsules were analyzed. No forming of chemical bond between the core material and the shell material was found during the microcapsule synthesis process. The latent heat and encapsulation efficiency of the microcapsules with addition of 0.5 mass% MnO 2 particles in the n-octadecane were measured at 107.5 ± 1.3 J g −1 and 95.3 ± 1.2%, respectively, which are higher than the microcapsules with pure n-octadecane, measured at 84.9 ± 1.2 J g −1 and 75.3 ± 1.4%, respectively. The thermal conductivity of the n-octadecane microcapsules modified with 0.5 mass% MnO 2 was enhanced by about 103.3% at 15.0 °C compared with the microcapsules without MnO 2 . Thermogravimetric and thermal cycling studies showed that the modified new microcapsules had good thermal stability. Such a modification provided an effective way to prepare phase-change energy storage microcapsules with better thermal properties and higher encapsulation efficiency.