Hollow silica spheres material（HSSM） with mesoporous wall and a specific surface area up to 951 m²/g were successfully synthesized, with dodecyl amine as the main template and with polyethylene glycol 1000 as the co-template. The effects of such synthesis conditions as temperature, concentration and solvent on the structure and morphology of HSSM were then investigated. The results show that   both the temperature and the solvent obviously influence the morphology and structure of HSSM;   at the optimal volume ratio of water to ethanol, namely 5： 2, hollow microspheres with smooth surface and high structure-ordering degree can be obtained;   a volume ratio higher than 6：1 or lower than 4：3 may result in irregular bulk with low ordering degree or mesoporous material with high ordering degree, respectively;   when the synthesis temperature is lower than the optimal one, namely 30 to 40 ℃, hollow microspheres cannot be obtained, while hollow microspheres may be destroyed when the temperature is higher than the optimal one; and   only when the mixed template concentration increases to 0. 038 mol/L can hollow microspheres-but not solid microspheres-be synthesized.