Thin film thermocouple (TFTC) is widely used in high temperature measurement, which is of short response time, less heat residual and integrated structure. Due to the ultra-thin structure of TFTC, the interfacial diffusion has a great influence on its reliability when exposed to high temperature environment, which leads to its performance degradation. Taking thermocouple on the turbine blade as research object, the parallel diffusion model of multilayer thermocouple is proposed based on Fick’s law. The reliability model of the protective layer, the sensitive layer and the insulating layer are established in the basis of the parallel diffusion model. According to the logical correlation among the multilayer films of TFTC, the TTF model of TFTC is given. Finally, an example of reliability model based on multilayer diffusion is simulated by Monte Carlo method, which demonstrates the feasibility of the method and model.