Using vehicle chassis information can significantly improve the accuracy of GNSS/INS fusion system when GNSS signals are unavailable. The IMU mounting angles play an important role when fusing vehicle chassis information with GNSS/INS system. However, the IMU mounting angles cannot be directly measured conveniently. This paper proposed a new method to simultaneously improve the estimation accuracy of both the vehicle heading angle and the IMU heading mounting angle by leveraging GNSS course angle as an additional measurement. Firstly, an error state Kalman filter is constructed with state variables including the attitude errors, velocity errors, position errors, gyro, and acceleration bias errors, IMU mounting angle and vehicle velocity scale factor. The GNSS course angle is augmented to the Kalman filter as a measurement when the vehicle travels in straight line. Then, the observability analysis of the GNSS/INS/Onboard sensors fusion system is carried out and the results show that the observability of the system using GNSS course angle is better than that of only using vehicle velocity and non-holonomic constraint (NHC) as measurements if the heading mounting angle and pitch mounting angle are not zero. Finally, the experiment results show that the accuracy of the vehicle heading angle and the IMU heading mounting angle can be improved by 14% judging from the lateral velocity error of vehicle compared to that of only using vehicle velocity and NHC as measurements.