In this paper, it is proposed to use a cylindrical cell for the characterization of dielectric material. The extraction of complex permittivity is based on inverse gradient approach where the full-wave simulation results are mapped to experimental data to extract the complex permittivity. As the operational frequency of radio frequency (RF)/microwave devices is increased, it becomes difficult to accurately model waveguide transitions using traditional methods based on meshing such as finite-element method (FEM) where mesh size is determined according to the wavelength. Moreover, these techniques usually require extensive computational resources. Mode matching technique (MMT) is the full-wave tool implemented in this current work. It is used to compute the generalized scattering matrices (GSMs) of the different discontinuities of test setup. These GSMs model precisely discontinuities as they include the effects of all higher-order modes propagating and evanescent. Simulation and experimental results are included to validate the proposed approach for the rigorous modeling of those discontinuities and hence the extraction of complex permittivity.