A one-port waveguide method and related apparatus based on the multi-state techniques is descried in this paper. This method measures only the magnitude and phase information for the reflection coefficients of four-state before and after the samples under test being loaded. On the basis of such data, the complex permittivity and permeability of the samples can be simultaneous calculated by software programmed according to the related theories discussed herein. In addition, the error analysis is also discussed in this paper. The proposed method is applicable to measure magnetic and/or medium-to high-loss materials, hence it is suitable to characterize the properties of radar absorbing materials.