Piezoelectric material, which exhibits excellent electro-mechanical conversion properties, is widely used in smart sensors and structures for sonar systems, weather detection and remote sensing. Hyperbolic shell structure made of piezoelectric material is liable to break down when it is used in high temperature environment, which is caused by the unexpected chaotic dynamic motion under the coupling effect of thermal filed and force field. Therefore, the chaotic nonlinear dynamic vibration of simply-supported piezoelectric material hyperbolic shell is studied under the combined action of temperature field and simple harmonic excitation. Based on the theory of finite deformation, the non-linear vibration equation and coordination equation of the hyperbolic shell are established. The non-linear dynamic equation of the structure is obtained by the Bubnov-Galerkin principle. The corresponding undisturbed Hamilton system has a homoclinic orbit. Using Melnikov function, the chaotic motion condition of the dynamic system under the criterion of Smale-horseshoe transformation is obtained. Furthermore, the mathematical model is established by Simulink software and the numerical simulations are performed by the fourth-order Runge-Kutta method. The simulation results accord well with those from the Melnikov method. The bifurcation diagram, the Lyapunov exponent diagram, the phase diagram and Poincaré section diagram are acquired to analyze the influence of temperature field on the non-linear characteristic of piezoelectric material hyperbolic shell system. When the temperature is close to 32℃ and 41℃, the Lyapunov index is less than 0 and the corresponding movement of the system is in the periodic zone, which is the same as that for a temperature range from 36℃ to 37℃. When the Lyapunov index is greater than 0, the corresponding movement of the system is in chaos zone. Therefore, the change of temperature has an additional effect on the stiffness of the system which affects the vibration of the system. The chaos and periodic zones of the system alternate with the increase of temperature and the vibration characteristics of the system can be controlled by changing the temperature field. Therefore, adjusting the temperature field can control the motion state of the system, which helps to improve reliability of the structure.