Novel inorganic-organic hybrid hollow nanospheres, acrylated SiO2 and SiO2@TiO2, were synthesized via a sol-gel polymerization, using crown-appended sugar gelator 1 as an organic template for the unique nanospherical structures in demand for a fast expanding area in nanomaterial research. In this work, hollow SiO2 nanospheres were obtained by a simple sol-gel method followed by calcination and rather rough TiO2 nanolayers were coated onto the highly dispersed surface of SiO2 nanospheres and further copolymerization of MPA on the surface of SiO2 and SiO2@TiO2 nanosphseres was successfully conducted. The morphological properties of those hollow nanospheres were characterized by TEM, SEM and powder-XRD. Furthermore, the physical and chemical properties of the synthesized nanocomposites were characterized by the analysis of EDX, FT-IR, TGA and ESCA.