This paper presents the implementation of the Bayesian inversion method for the characterization and estimation of different dielectric material properties. The scattering parameters of single and multi-layer materials are measured using a free-space experimental setup using a standard gain horn antenna and a Vector Network Analyzer (VNA) at Ka-band (26–40 GHz). The relative permittivity, material thickness, and material positioning error are defined as model parameters and estimated using the observed (measured) data. The FR4 Epoxy, Rogers RT/Duriod 5880, and Rogers AD600 with different relative permittivities and thicknesses are used in the measurement setup. The results displayed good agreement between model parameters and estimated properties of the presented materials, while the corresponding eigenvectors provided a level of confidence in model parameter values. The results were compared with different reported techniques to showcase the possible use of the presented method in microwave imaging, non-destructive testing, and similar applications.