Flexible electronic devices, which are based on thin film/substrate structure, have excellent stretchability and sensitivity, but the dynamic behaviour of this film/substrate structure is very susceptible to the complex excitation such as temperature change. Therefore, the dynamic buckling behaviour of thin film/substrate structure under the thermal effect is studied in this paper. Firstly, based on Euler-Bernoulli beam theory, the governing equations of nonlinear vibration of thin film/substrate structure under the thermal effect are established. Secondly, the governing equations of nonlinear vibration of thin film/substrate structures are introduced into Hamilton system by the Galerkin method. Finally, the Hamilton equation of the thin film/substrate structure is solved by the Symplectic Runge-Kutta method, and the influence of temperature variation and damping coefficient on the nonlinear dynamic response of the thin film/substrate structure is discussed. It is found that the temperature variation and the pre-strain could change the dynamic behaviour of the thin film/substrate structure. With the increase of temperature variation, the vibration frequency of the film/substrate structure increases and the amplitude decreases. With the increase of pre-strain, the frequency of the system decreases and the amplitude increases.