An effective method to synthesize organosilica hollow sphere (OSHS) is achieved by direct co-condensation of tetraethoxysilane and organosiloxane template, 3-(2-butylidene)aminopropyltrimethoxysilane (BAPTMS). 1-Decanol dispersed in ammonia solution creates hydrophobic cores for the direct deposition of silica. Simultaneously, BAPTMS dissolves in oily droplets, and caps with highly reactive methoxy groups to produce hollow structure. The obtained OSHS has mesoporous structure with a specific surface area of 137 m2/g. This method ignores the utilization of shell structure-directing agent and thus prevents complicated template removal process.