A method for determining the parameters of a layered semiconductor structure, using the data obtained by near-field microwave probing with a micron-size lateral resolution, was developed and tested experimentally. We have measured a frequency spectrum of the impedance of a coaxial antenna formed on a test structure surface. The corresponding inverse problem has been solved based on the quasistatic theory for the impedance of a monopole antenna interacting with a layered medium, which was proposed earlier [A. N. Reznik and S. A. Korolyov, J. Appl. Phys. 119, 094504 (2016)]. This method was applied to a low-barrier Mott diode structure with a nearly 100 nm thick undoped layer grown on a conducting substrate GaAs. Computer simulation allowed us to establish the optimal frequency intervals and estimate the accuracy of determining the structure parameters. Measurements were taken in the frequency range of 0.1–67 GHz on commercially available equipment. Three antennas with a radius of the central conductor of 5.5, 11, and 25 μm, respectively, were used. The accuracy of the experimental evaluation of the layer thickness d and conductivity σ was ∼1–3%, and for the substrate conductivity, it came to about 15%. As an example, we also present the parameters σ and d in four points of the sample surface image. These data show strong lateral inhomogeneity of the structure under study.