Polarization observation of sky radiation is the frontier approach to improve the remote sensing of atmospheric components, e.g., aerosol and clouds. The polarization calibration of the ground-based Sun-sky radiometer is the basis for obtaining accurate degree of linear polarization (DOLP) measurement. In this paper, a DOLP calibration method based on a laboratory polarized light source (POLBOX) is introduced in detail. Combined with the CE318-DP Sun-sky polarized radiometer, a calibration scheme for DOLP measurement is established for the spectral range of 440-1640 nm. Based on the calibration results of the Sun-sky radiometer observation network, the polarization calibration coefficient and the DOLP calibration residual are analyzed statistically. The results show that the DOLP residual of the calibration scheme is about 0.0012, and thus it can be estimated that the final DOLP calibration accuracy of this method is about 0.005. Finally, it is verified that the accuracy of the calibration results is in accordance with the expected results by comparing the simulated DOLP with the vector radiative transfer calculations.