In this study, Li3AlF6 was employed to simulate the molten salt LiF–BeF2 to explore its pyrohydrolysis behavior and that of its components, i.e., LiF and AlF3, respectively. The influence of the accelerators α-Al2O3 and AlF3 on the pyrohydrolysis of LiF and Li3AlF6 was investigated. Finally, the solid pyrohydrolytic products were characterized by means of X-ray diffraction, and the corresponding reaction mechanisms were proposed. These experimental results indicated that AlF3 was completely hydrolyzed to the corresponding oxide α-Al2O3 at 650 °C in 1 h, whereas the complete hydrolysis of LiF and Li3AlF6 required the assistance of either α-Al2O3 or AlF3 under the same conditions. The influence of the accelerator α-Al2O3 and AlF3 on the pyrohydrolytic behavior of Li3AlF6 provides references for future research studies on the pyrohydrolysis of LiF–BeF2 and multi-component molten salts. © 2018, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Chinese Nuclear Society, Science Press China and Springer Nature Singapore Pte Ltd.