Accurate estimation of sideslip angle is essential for vehicle stability control. For commercial vehicles, the estimation of sideslip angle is challenging due to severe load transfer and tire nonlinearity. This paper presents a robust sideslip angle observer of commercial vehicles based on identification of tire cornering stiffness. Since tire cornering stiffness of commercial vehicles is greatly affected by tire force and road adhesion coefficient, it cannot be treated as a constant. To estimate the cornering stiffness in real time, the neural network model constructed by Levenberg-Marquardt backpropagation (LMBP) algorithm is employed. LMBP is a fast convergent supervised learning algorithm, which combines the steepest descent method and gauss-newton method, and is widely used in system parameter estimation. LMBP does not rely on the mathematical model of the actual system when building the neural network. Therefore, when the mathematical model is difficult to establish, LMBP can play a very good role. Considering the complexity of tire modeling, this study adopted LMBP algorithm to estimate tire cornering stiffness, which have simplified the tire model and improved the estimation accuracy. Combined with neural network, A time-varying Kalman filter (TVKF) is designed to observe the sideslip angle of commercial vehicles. To validate the feasibility of the proposed estimation algorithm, multiple driving maneuvers under different road surface friction have been carried out. The test results show that the proposed method has better accuracy than the existing algorithm, and it’s robust over a wide range of driving conditions.