To characterize the linear birefringence of a multiple-order wave plate (MWP), an oblique incidence is one of the methods available. Multiple reflections in the MWP are produced, and oscillations in the phase retardation measurement versus the oblique incident angle are then measured. Therefore, an antireflection coated MWP is required to avoid oscillation of the phase retardation measurement. In this study, we set up a phase-sensitive heterodyne ellipsometer to measure the phase retardations of an uncoated MWP versus the oblique incident angle, which was scanned in the x–z plane and y–z plane independently. Thus, the effect on multiple reflections by the MWP is reduced by means of subtracting the two measured phase retardations from each other. As a result, a highly sensitive and accurate measurement of retardation parameters (RPs), which includes the refractive indices of the extraordinary ray n_e and ordinary ray n_o , is obtained by this method. On measurement, a sensitivity \left(n_e,n_o\right) of {10}^{-6} was achieved by this experiment setup. At the same time, the spatial shifting of the P and S waves emerging from the MWP introduced a deviation between experimental results and the theoretical calculation.