In the current study, the molecular structures of the two new azomethine dyes such as AAFOH-1 and AAFOH-2 have been investigated with the use of density functional theory (DFT/B3LYP/6-311+G(d)) in a DMSO solvent for the first time. The electronic spectra of the new dyes in a DMSO solvent were carried out by temporally dependent density functional theory (TD-DFT) method. The computed absorption spectral data of the investigated molecules are in good agreement with the experimental data, thus allowing an assignment of the UV/Vis spectra. The equilibrium geometry, the HOMO and LUMO molecular orbitals, excitation energies, oscillator strengths and natural bond orbital (NBO) analysis for the molecules have also been calculated and presented. The electron location function (ELF), localized orbital locator (LOL), and quantum theory of atoms in molecules (QTAIM) analyses were also carried out. On the basis of polyvinyl alcohol (PVA) and the new synthesized azomethine dyes polarizing films were developed. The main optical parameters of polarizing PVA-films (transmittance, polarization efficiency, and dichroic ratio) have been measured and discussed. Anizotropy of thermal conductivity of the PVA-films have been studied.