In this paper, GNSS interferometric reflectometry (GNSS-IR) is firstly proposed to estimate ground surface subsidence caused by underground coal mining. Ground subsidence on the main direction of a coal seam is described by using the probability integral model (PIM) with unknown parameters. Based on the laws of reflection in geometric optics, model of GNSS signal-to-noise (SNR) observation for the tilt surface, which results from differential subsidence of ground points, is derived. Semi-cycle SNR observations fitting method is used to determine the phase of the SNR series. Phase variation of the SNR series is used to calculate reflector height of ground specular reflection point. Based on the reflector height and ground tilt angle, an iterative algorithm is proposed to determine coefficients of PIM, and thus subsidence of the ground reflection point. By using the low-cost navigational GNSS receiver and antenna, an experimental campaign was conducted to validate the proposed method. The results show that, when the maximum subsidence is 3076 mm, the maximum relative error of the proposed method-based subsidence estimation is 5.5%. This study also suggests that, based on the proposed method, the navigational GNSS instrument can be treated as a new type of sensor for continuously measuring ground subsidence deformation in a cost-effective way.