Abstract: Solid catalyst added with tung shell ash(KOH-TSA-Al2O3) was prepared using Al2O3 and KOH as raw materials. The catalyst was used in the process of methyl esterification of tung oil. Its catalysis efficiency was analyzed. Effects of KOH dosage, sintering temperature and tung shell ash dosage on the conversion efficiency of tung oil were studied with the solo conditions experiment and orthogonal design. The final results showed that the efficiency of methyl esterification catalyzed by the optimized solid catalyst was up to 76.34%, under the conditions of 6 g KOH, 4 g Al2O3, 3 g tung shell ash, and 700℃ for 10 h. The prepared catalyst was analyzed with alkalinity detected, scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that the surface catalyst was like tree branch and new phase of CaO, MgO and SiO2 was generated. Compared with 0# diesel standard in China, the biodiesel prepared under the catalyst was showed better quality.