Spherical alumina powders were prepared by the controlled hydrolysis of aluminum iso-propoxide in a solution consisting of n-octyl alcohol and acetonitrile. As aluminum alkoxide's concentration increased, the particle size was increased and size distribution was more broad. As-prepared particle morphology was not spherical when acetonitrile volume fraction was increased over than 60%. As-prepared amorphous powders crystallized to γ-alumina at 1000℃ and converted to α-alumina at 1150℃. The particle morphology was retain after crystallization α-alumina. When aluminum iso-propoxide was used as aluminum source, the optimum preparation condition of spherical alumina was 0.1M AIP, 0.2M H2O, 0.1g/l HPC with a volume fraction (1/1) of the n-octyl alcohol/acetonitrile, 10min of reaction time and 30min of aging time.