GNSS-R has recently emerged as a new prosperous remote sensing tool in ocean surface, snow/ice surface and land surface. In this paper, the possible application in sensing the bare soil freeze-thaw process is investigated with GNSS-R. The Fresnel reflectivity from the wave synthesis technique is used to get the circular polarization reflectivity. Large differences are found for the Fresnel reflectivities at V, H, RR polarizations during bare soil freeze-thaw process, but there are almost no differences as for LR polarization. Therefore if a special GNSS-R receiver is designed, the reflected signals of RR polarization should be efficiently used. For GPS multipath reflectometry, the improved Fresnel reflectivity is inserted into the fully polarimetric forward multipath model to get the simulated GPS L1 observables: SNR, carrier phase multipath error and pseudorange code multipath error, which are used to estimate the bare soil freeze-thaw process. Compared to the thawed soil, the amplitudes of GPS observables are smaller for the frozen soil. Therefore, it is possible to monitor bare soil freeze-thaw process with ground geodetic GPS receivers.