Hollow ceramic microspheres of A1 2 O 3 , SiO 2 , and mullite have been prepared by the combination of an emulsion technique with a water extraction sol-gel method. Concentration of sol, initial droplet size, and water extraction rate of the system are found to be the important process parameters controlling the size and wall thickness of the hollow microspheres, and their influences are shown. A model that correlates the morphology of microspheres to concentration and water extraction rate is proposed and is in good agreement with the experimental observations. The capability and limitation of this process for forming hollow microspheres are demonstrated. It was shown that hollow microspheres with sizes greater than 5 fim could be readily prepared, while a limitation was met for sizes less than 1 /xm, in which case solid microspheres were normally formed.