The effect of the addition of various fluoreides on the mullitization of Korean crude kaolin was studied by X-ray powder diffraction and scanning electron microscopic methods. Kaolin without any addition of fluoreides began to be transformed into the mullite at 1, 10$0^{circ}C$. Mullite peaks were discernible in the X-ray diffraction patterns of the specimens which contained fluorides equivalent to about 2 wt % fluorine, and which were sintered at 1, 05$0^{circ}C$. The higher the concentration of fluorine in kaolin, the lower was the initiatinig temperature of mullitization. Experiments , for example, showed that mullite could be formed at 95$0^{circ}C$ from kaolin mixed with 3.4% fluorine. Of the fluoride, addtives, sodiumsiliconfluoride $(Na_2SiF_6)$ was must effective in mullite formation of kaolin. In order of accelerating mullitization, the fluorides except $Na_2SiF_6$ could be placed in following sequence ; (1) sodium (NaF) (2) aluminium$(AlF_3)$ (3)potassium(KF) (4) ammonium$(NH_4F)$ (5) magnesium$(MgF_2)$ (6) calcium$(CaF_2)$. It was considered that the intrinsic characteristics of fluorides, such as size of ionic radiu, charge , bond strength between cation and anion, and electronegativity of cation affected millitization of halloysite, a main constituent mineral of kaolin.