To provide meaningful data, polarimetric ground penetrating radar (GPR) requires accurate calibration of channel imbalance and crosstalk not only in the amplitude term but also in the phase term. Currently, calibration techniques usually ignore higher-order terms to simplify equations. These techniques, though very easy to perform, provide less accurate calibration results for the crosstalk. To improve the accuracy of calibration, we have derived a new mathematical formulation to calibrate a polarimetric GPR system. We measured several scattering matrices to obtain the necessary calibration parameters. The calibration technique was tested from measurements conducted on a 22.5° oriented dihedral corner reflector from 1 to 6 GHz with a step of 0.1 GHz. The calibrated results are found to be consistent with the theoretically values, especially for the crosstalk.