The integration of strapdown inertial navigation system (SINS) and laser Doppler velocimeter (LDV) is a reliable technology for land vehicle positioning. To ensure the best positioning performance of the SINS/LDV integrated navigation system, it is necessary to calibrate it accurately. However, the accuracy of the error model of the traditional calibration method is seriously affected by the large misalignment angle, which in turn affects the accuracy and consistency of the filtering, and eventually leads to the decline of the calibration accuracy. Therefore, this paper introduces the Lie group theory for the first time into the calibration study of the SINS/LDV integrated navigation system. Based on the error state vector defined by the left group error definition in the Lie group, the three calibration models of the SINS/LDV integrated navigation system are derived in the Earth-centered Earth-fixed frame, using velocity, displacement increment, and dead reckoning (DR) position, which are the three common observation information. The most significant advantage of these calibration models is their ability to handle large initial misalignment angles. The calibration models proposed in this paper are comprehensively evaluated by two long-distance vehicle experiments. The test results show that under normal conditions (no large attitude misalignment angle and all sensors are working properly), the Lie group-based calibration methods have similar performance to the traditional calibration method, but they have significant advantages in the case of large initial attitude deviation. In addition, using displacement increment and DR position as observations improves calibration performance compared to velocity.