This study is targeted at the key state parameters of vehicle stability controllers, the controlled vehicle model, and the nonlinearity and uncertainty of external disturbance. An adaptive double-layer unscented Kalman filter (ADUKF) is used to compute the sideslip angle, and a vehicle stability control algorithm adaptive fuzzy radial basis function neural network sliding mode control (AFRBF-SMC) is proposed. Since the sideslip angle cannot be directly determined, a 7-degrees-of-freedom (DOF) nonlinear vehicle dynamic model is established and combined with ADUKF to estimate the sideslip angle. After that, a vehicle stability sliding mode controller is designed and used to trace the ideal values of the vehicle stability parameters. To handle the severe system vibration due to the large robustness coefficient in the sliding mode controller, we use a fuzzy radial basis function neural network (FRBFNN) algorithm to approximate the uncertain disturbance of the system. Then the adaptive rate of the system is solved using the Lyapunov algorithm, and the systemic stability and convergence of this algorithm are validated. Finally, the controlling algorithm is verified through joint simulation on MATLAB/Simulink-Carsim. ADUKF can estimate the sideslip angle with high precision. The AFRBF-SMC vehicle stability controller performs well with high precision and low vibration and can ensure the driving stability of vehicles.