Accurate estimation of vehicle states is extremely crucial for vehicle stability control. As a reliable estimation methodology, the unscented Kalman filter (UKF) has been widely utilized in vehicle control. However, the estimation accuracy still needs to be improved caused by the unpredictable measurement and process noise. In this paper, a novel modified UKF state estimation methodology combined with the ant lion optimization (ALO) is proposed for the stability control of a four in-wheel motor independent drive electric vehicle (4WIDEV). First, the optimal performance of the ALO algorithm is analyzed, where both unimodal and multimodal optimization test functions are selected and optimized by GA, PSO, and ALO, respectively. The results indicate that the ALO algorithm has good global optimization capability and applicability. Second, the ALO algorithm is merged into the UKF to adjust the statistical properties of noise information for the ALOUKF estimator design without extra sensor signals. At last, the simulations on the Matlab/Simulink-CarSim co-simulation platform and the road test based on an A&D 5435 rapid prototyping experiment platform (RPP) are carried out to verify the proposed method. The simulation and experiment results demonstrate that the ALOUKF estimator can improve state estimation accuracy and resist the vehicle nonlinearity even in the case of the complicated and emergency maneuvers.