In order to solve the problem that the control system of permanent magnet synchronous motor (PMSM) is difficult to meet the high control accuracy due to the influence of non-repeated disturbances such as external disturbance, system parameter variation, and friction force during operation, a novel sliding mode control (NSMC) method based on tracking differentiator (TD) and radial basis (RBF) neural network was proposed. Firstly, a new sliding mode reaching law is proposed by adding the state variables to the traditional exponential reaching law, which can effectively reduce the chattering of the system. Then, the speediest tracking differentiator is designed to estimate the given speed signal and its differential signal, to realize the novel sliding mode variable structure algorithm. Finally, the RBF neural network is used to compensate for the uncertainty and external interference of the system; the robustness of the system is further improved by adaptive weight updating. The simulation results show that, by comparing with the traditional exponential approach law, the overshoot of 22 r/min is reduced by the control method based on the new hybrid reaching law, the speed decrease amplitude is reduced by 77.1% under load disturbance, and the speed recovery time is shortened by 0.059 s. After the optimization of the new sliding mode control method based on tracking differentiator and RBF neural network, the overshoot of 86 r/min is further reduced, the speed decrease amplitude of load disturbance is reduced again by 48.5%, and the speed recovery time is shortened again by 0.073 s.