A polarimetric method is proposed to determine the tilt angle of the local optical axis of a liquid crystal at layer boundaries. The method is based on the measurement of the azimuthal polarization angles of light waves passed through a liquid-crystal cell or reflected from it. This method requires neither the knowledge of the refractive indices of a liquid crystal nor the homogeneity of the layer. The method can be applied in the whole range of tilt angles. Experimental data on the measurement of the tilt angles in cells assembled by the scheme of a prism liquid-crystal polarizer are presented.