In the past two decades, global navigation satellite system-reflectometry (GNSS-R) has emerged as a new remote sensing technique for soil moisture monitoring. Some experiments showed that the antenna of V polarization is more favorable to receive the reflected signals, and the interference pattern technique (IPT) was used for soil moisture and retrieval of other geophysical parameters. Meanwhile, the lower satellite elevation angles are most impacted by the multipath. However, electromagnetic theoretical properties are not clear for GNSS-R soil moisture retrieval. In this paper, the advanced integral equation model (AIEM) is employed using the wave-synthesis technique to simulate different polarimetric scatterings in the specular directions. Results show when the incident angles are larger than 70°, scattering at RR polarization (the transmitted signal is right-hand circular polarization (RHCP), while the received one is also RHCP) is larger than that at LR polarization (the transmitted signal is RHCP, while the received one is left-hand circular polarization (LHCP)), while scattering at LR polarization is larger than that at RR polarization for the other incident angles (1°∼70°). There is an apparent dip for VV and VR scatterings due to the Brewster angle, which will result in the notch in the final receiving power, and this phenomenon can be used for soil moisture retrieval or vegetation corrections. The volumetric soil moisture (vms) effects on their scattering are also presented. The larger soil moisture will result in lower scattering at RR polarization, and this is very different from the scattering of the other polarizations. It is interesting to note that the surface correlation function only affects the amplitudes of the scattering coefficients at much less level, but it has no effects on the angular trends of RR and LR polarizations.