Silica microcapsules with hierarchical pore structure are prepared using a one step emulsion templated hydrolysis method. Silica particles of around 100 nm with percolated nanosized pores are self-assembled into micrometer scale spherical shells. The porous structure serves as an ideal host for shape stabilization of melted organic compounds. Small angle X-ray scattering (SAXS) results show that the n-eicosane encapsulated in nanoporous silica consists of mass fractal structure with a fractal dimension of 2.1. n-Eicosane encapsulated in the nanosized pores exhibits novel phase change behavior. A large melting point drop from 37.0 to 28.8 °C is observed, which is attributed to the strong interaction between the n-eicosane molecules and the silica skeleton.