The effective reflection coefficients of an obliquely incident wave on a multi-layered substrate coated with a uniaxially anisotropic alignment layer are derived. The effective reflection coefficients as well as explicit ellipsometric expressions are provided as a function of film constants of multiple layers together with magnitude of anisotropy, direction of optic axis, and thickness of the alignment layer. It is expected that by adapting these expressions to the conventional modelling technique, the ordinary refractive index, the extra-ordinary refractive index, the azimuth angle and the tilt angle of the optic axis, and the thickness of the aligned surface can be determined simultaneously together with the thickness and volume fraction of each layer beneath the alignment layer.