Path tracking error control is an essential functionality in the development of autonomous vehicles to follow a planned trajectory. Significant path tracking errors could lead to a collision or even out of the control of the vehicle. Model-based control strategies have been developed to minimize the vehicle’s path tracking errors. However, the vehicle model may not truly represent the actual vehicle dynamics. Furthermore, the parameters employed in the vehicle dynamic model may not represent the actual operating conditions of the vehicle under environmental uncertainty. This paper proposes a real-time bias-learning method coupling with the model predictive control (MPC) to improve the fidelity of a baseline vehicle model with the aid of a few experiments (or virtual experiments) so that the path tracking error can be reduced in real-time operation. Gaussian process (GP) regression and recurrent neural network (RNN) are employed for bias-learning and their effectiveness are compared under different scenarios. GP regression learns non-linearity of the model bias through its nonlinear kernel function, whereas the RNN model formulates the bias as a linear combination of hidden nodes which capture the non-linearity of the model bias with a recurrent form. Results reveal that RNN is more effective for real-time learning of the nonlinear model bias than the classical GP regression and the proposed bias-learning model is able to improve the fidelity of a baseline vehicle dynamic model. Consequently, path tracking performance can be greatly improved under environmental uncertainty using the bias-learning-based MPC.