Various inorganic fillers improve the thermal conductivity and physical properties of organic products. Alumina has been used a representative filler in the heat radiation sheet for the heat radiation of electric device. The high filling rate of alumina increases the thermal conductivity and properties of products. We successfully developed the spherical alumina by flame fusion process using the oxygen burner with LPG fuel. In the high temperature flame (25003000) of oxygen burner, sprayed powders were melting and then rotated by carrier gas. This surface melting and rotation process made spherical alumina. Especially effects of chemical composition and particle size of stating materials on the melting behavior of starting materials in the flame and spheroidization ratio were investigated. As a result, spheroidization ratio of boehmite and aluminum hydroxide with endothermic reaction of dehydration process was lower than that of the sintered alumina without dehydration reaction.