A series of microencapsulated phase change materials with an organic/inorganic composite shell was designed for obtaining excellent thermal compactness and thermal stability. The capsule wall was obtained via hydrolyzing ethyl orthosilicate with melamine resin as the hard template to MF/SiO2 materials for encapsulation n-octadecane. The results of chemical analysis and structure characterizations indicated that MF/SiO2 microcapsules with an obvious core-shell microstructure were successfully fabricated. The thermal conductivity of MF/SiO2 microcapsules is raised to 30.05% via comparing with original microcapsules. The microcapsules obtained present excellent latent heat storage and release properties (Delta H-m = 167.1 J.g(-1)). The enthalpy value of the synthetic microcapsule hardly changed from 164.5 to 162.9 J.g(-1) after extraction, indicating that the microcapsules have distinguished sealing performance. In addition, the MF/SiO2 microcapsules still presented noteworthy thermal cycle durability.