Ludwigite is the main available boron-bearing resource in China. In order to enrich the theory system and optimize its utilization processes, this paper study the mechanism and kinetics on non-isothermal decomposition of ludwigite in inert atmosphere by means of thermal analysis. Results show that, the decomposition of serpentine and szajbelyite is the main cause of mass loss in the process. At the end of decomposition, hortonolite and ludwigite are the two main phases in the sample. The average E value of structural water decomposition is 277.97 kJ/mol based on FWO method (277.17 kJ/mol based on KAS method). The results is proved to be accurate and reliable. The mechanism model function of structural water decomposition is confirmed by Satava method and Popescu method. The form of the most probable model function is G(α) = (1 – α)–1 – 1 (integral form) and f (α) = (1 – α)2 (differential form), and its mechanism is chemical reaction. This is verified by the criterion based on activation energy of model-free kinetics analysis.