Underwater acoustic technology is essential for ocean observation, exploration and exploitation, and its development is based on an accurate predication of underwater acoustic wave propagation. In shallow sea environments, the geoacoustic parameters, such as the seabed structure, the sound speeds, the densities, and the sound speed attenuations in seabed layers, would significantly affect the acoustic wave propagation characteristics. To obtain more accurate inversion results for these parameters, this study presents an inversion method using the waveguide characteristic impedance based on the Bayesian approach. In the inversion, the vertical waveguide characteristic impedance, which is the ratio of the pressure over the vertical particle velocity, is set as the matching object. The nonlinear Bayesian theory is used to invert the above geoacoustic parameters and analysis the uncertainty of the inversion results. The numerical studies and the sea experiment processing haven shown the validity of this inversion method. The numerical studies also proved that the vertical waveguide characteristic impedance is more sensitive to the geoacoustic parameters than that of single acoustic pressure or single vertical particle velocity, and the error of simulation inversion is within 3%. The sea experiment processing showed that the seabed layered structure and geoacoustic parameters can be accurately determined by this method. The root mean square between the vertical waveguide characteristic impedance and the measured impedance is 0.38dB, and the inversion results accurately represent the seabed characteristics in the experimental sea area.