The hollow ceramic microspheres were prepared by Self-reactive flame spraying method. The structural characteristics and morphology properties of the composite powders were obtained by XRD and SEM. The results show that the obtained particles are hollow ceramic microspheres. The average particle size is about 30μm. An analytical method for the determination of electromagnetic parameters (ε, μ) of materials under test is presented by the analysis of normalized general matrix of equivalent network of coaxial line filled with samples. The analysis of vector network analyzer show that reflectance of hollow composite microspheres could well absorb microwaves in 2-18 GHz. The reflection loss is less than -l0dB in the range of 12.4 to15.2GHz while the minimum reflection loss is -18.5dB at 13.6GHz.