The critical angle at which the brightness of oil slicks and oil‐free seawater is reversed occurs under sunglint and is often shown as an area of uncertainty due to different roughness and surface Fresnel reflection parameters. Consequently, differentiating oil slicks from the seawater in these areas using optical sensors is a challenge. Polarized optical remote sensing techniques provide complementary information for intensity imagery with different physical properties and, thus, possess the ability to resolve this difficult problem. In the polarized reflectance model, the degree of linear polarization (DOLP) of sunglint depends on accurately knowing the Stokes parameter for the reflected light, and varies with the refractive index of the surface layer and viewing angles. For the polarized detection of oil slicks, the highest sensitivity of the DOLP to the refractive index is located within the specular reflection direction where the sum of the solar and sensor zenith angles is 82.6°. The modeled results clearly indicate that the DOLP of oil slicks is weaker in comparison with oil‐free seawater under sunglint. Using measurements from the space‐borne Polarization and Anisotropy of Reflectances for Atmospheric Sciences coupled with Observations from a Lidar (PARASOL) over the Deepwater Horizon oil spill in the Gulf of Mexico, we illustrate that the PARASOL‐derived DOLP difference between the oil spill and seawater is obvious and is in accordance with the modeled results. These preliminary results suggest that the potential of multiangle measurement and feasibility of deriving refractive index of ocean surface from space‐borne sensors need further researches.