This chapter reviews the application and characterization of material that uses the microwave waveguide systems. For macroscopic characterization, three properties of the material are often tested: complex permittivity, complex permeability and conductivity. Based on the experimental setup and sub-principle of measurements, microwave measurement techniques can be categorized into either resonant technique or nonresonant technique. In this chapter, calibration procedures for non-resonant technique are described.The aperture of open-ended coaxial waveguide has been calibrated using Open-Short-Load procedures. On the other hand, the apertures of rectangular waveguides have been calibrated by using Short-Offset-Offset Short procedures and Through-ReflectLine calibration kits. Besides, the extraction process of complex permittivity and complex permeability of the material which use the waveguide systems is discussed. For one-port measurement, direct and inverse solutions have been utilized to derive complex permittivity and complex permeability from measured reflection coefficient. For two-port measurement, in general, the material filled in the waveguide has been conventional practice to measure the reflection coefficient and the transmission coefficient by using NicholsonRoss-Weir (NRW) routines and convert these measurements to relative permittivity, ε r and relative permeability, μ r . In addition, this chapter also presents the calculation of dielectric properties based on the difference in the phase shifts for the measured transmission coefficients between the air and the material.