The sun glint has been proven to be a valuable natural polarization calibration target because it is strongly polarized, and its polarization characteristics can be accurately simulated with models. It is convenient to calibrate the satellite’s in-flight polarimetry by comparing the polarization simulations with actual measurements. Meanwhile, the accuracy of polarization simulation at the top of the atmosphere (TOA) over sun glint is affected by several atmospheric and oceanic surface factors and depends on the specific solar-viewing geometry. In this paper, the sensitivity of the degree of linear polarization (DOLP) at the TOA to the uncertainties of the aerosol optical depth, aerosol model, absorption gas content (CWV, O3), sea surface instantaneous wind speed (WS), and chlorophyll concentration (Chl) under different solar-viewing geometries is analyzed via radiative transfer simulation. The error budgets indicate that aerosols and WS are the main error factors for polarization calibration, while the uncertainties of Chl and absorbing gases can be disregarded. The total DOLP error increases with the solar zenith angle and viewing zenith angle (i.e., the increase of atmospheric optical path) and the sun glint angle (SGA, the angle between the viewing and the specular directions of the sun) (i.e., the decrease of sun glint brightness). The dependence of the total DOLP error on SGA decreases with the WS (i.e., the increase of sun glint spot area and the decrease of the sun glint intensity) and increases with the wavelength (i.e., the decrease of atmospheric scattering contribution). Based on the error budgets, an optimized solar-viewing geometry screening strategy is proposed to ensure that the simulated DOLP error is limited to 0.02. The in-flight DOLP calibration result of POLDER/PARASOL shows that the proposed screening strategy obtained more calibration samples and covered a wider range of DOLP, especially for the samples with DOLP of less than 0.2, compared with the screening strategies of Toubbe et al. [IEEE Trans. Geosci. Remote Sens. 37, 513 (1999)IGRSD20196-289210.1109/36.739104]and Hagolle et al. [IEEE Trans. Geosci. Remote Sens. 42, 1472 (2004)IGRSD20196-289210.1109/TGRS.2004.826805] in previous work. The smaller standard error (SE) of the samples indicates more stable calibration results obtained for the optimized strategy. This research presents an optimized strategy for screening the solar-viewing geometry of the samples to calibrate satellite in-flight polarization measurements using the sun glint.