Future optical technologies are basically depending on and employing different types of optical waveguides. The fabrication of waveguides with different properties represents an expanding direction in both the industrial and scientific fields. In the current paper, we focus on studying the polymeric planar waveguides fabricated by the method of UV–excimer–laser lithography. We propose a general technique based on the WKB approximation and digital holographic interferometry to characterize slab waveguides with arbitrary refractive index profile. The necessary theoretical model is derived and the characterization method given in detail. Two samples are fabricated from polymethylmethacrylate (PMMA) polymeric material using different parameters for the used UV-laser. Then a phase-shifting digital holographic technique with the help of a Mach–Zehnder-like interferometer, is used to characterize the samples and measure their modified refractive index profiles. The resulting profiles are then fed to the proposed theoretical model and a full TE mode analysis is obtained. These results prove the ability of the proposed technique to analyze planar waveguides having any complicated refractive index profile.