High refractive index (RI) thin films are capable of pulling waveguide mode profiles towards themselves. In this study, it is shown that by applying high RI coatings with specific thicknesses on the side of optical waveguides, significantly different mode profiles for orthogonal polarizations can be achieved. This phenomenon, that we call it polarization-selective mode shaping, can be extensively used in the enhancement of polarization-dependent integrated optical devices. As an illustrating application, a tri-layer structure consisting of poly(methyl methacrylate)/graphene/chalcogenide on a side-polished fiber is designed to realize an extremely high extinction ratio polarizer. This structure changes the mode profiles in a way that the attenuation of TE mode is maximized, while the power carried by the TM mode remains relatively constant. Simulations and experimental characterizations confirm that polarization-selective mode shaping coordinates four loss mechanisms to maximize the extinction ratio and minimize the insertion loss of the polarizer. The fabricated polarizer is examined in the O, C, and L telecommunication frequency bands. This configuration achieves the high extinction ratio of 51.3 dB and its maximum insertion loss in the tested wavelengths is 1.79 dB. The proposed polarizer has been compared with other state-of-the-art polarizers in the conclusion section which shows its superiority.