In this report, we describe the photo-induced in-plane alignment of nematic liquid crystal (LC) molecules, 5CB, in a hybrid cell with alternate self-assembled films of low-molecular weight azobenzene dye and polyelectrolyte on gold electrodes using the attenuated total reflection (ATR) measurement method. The molecular self-assembly process was also investigated by the ATR method. Reflectivities due to excitations of the surface plasmon polariton (SPP) were observed in the ATR properties of the LC cell. In-plane switching of the LC molecules adjacent to the aligning layer was evaluated from the ATR curves after irradiation of linearly polarized visible light to the LC cell. The sensitivity of the ATR method gives information on the alignment, tilt angle, and extent of LC reorientation in the bulk. Thus, the importance of using the molecular self-assembly processes of individual polyion-dye pairs for fabrication of new photo-aligning layers is emphasized.