High-speed digital microsystems has emerged as one of the most important solutions for improving system performance, bandwidth, and power consumption. Based on mature micro-system processing technology, a material extraction approach for silicon interposer applied for high-speed digital microsystems was presented in order to obtain frequency-dependent precise material parameters. By combining microwave theory and mathematical model of iterative algorithm, the dielectric constant (Dk) and the dissipation factor (Df) of polyimide dielectric layer is acquired, which minimizes testing costs and streamlines testing process. The method is based on two-port transmission/reflection measurements. Vector Network Analyzer (VNA) is used to extract the scattering parameters with an extraction range of 1 MHz to 10 GHz. The algorithm is programmed using MATLAB. The observed Dk values at 2 GHz, 6 GHz, 8 GHz, and 10 GHz are, respectively, 3.22, 3.04, 2.96, 3.03, and 2.91, while the corresponding Df values are 0.021, 0.025, 0.026, 0.026, and 0.024. Finally, the complex permittivity derived is simulated and analyzed using Ansys HFSS. The results verify the validity of the theoretical method and proves that the values of the complex permittivity obtained by the method in this paper are reliable.