Preparation of porous silica from thermally activated kaolinite was investigated by using acid dissociation process, and the relationship between structural transformation and acid dissociation properties of aluminium were elucidated. AlVI transfers into AlV and AlIV when kaolinite changes into metakaolinite during thermal activation. AlV is dissoluble in acid, while AlVI, AlIV are difficult to be dissolved into acid, therefore, the coordinations of aluminium affect acid dissociation of alumina markedly. Mesoporous silica is made by acid dissociation alumina of metakaolinite, and the specific surface area of porous silica is determined by acid dissociation ratio of alumina. The dissociation ratio of aluminum is up to 97% when kaolinite is activated at 900°C for 15 min. Specific surface area of the porous silica material is 357 m2/g, the pore volume is 0.43 cc/g, and BJH pore diameter is 2.18 nm. The pore is found to be in the worm-like shape by high resolution TEM analysis.