In this article, new experimental results of the morphological and optical properties of thin films of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran co-doped by 8-hydroxyquinoline zinc (Znq2) for different concentrations were presented. The physical vapor deposition in a high vacuum was used to create the thin films on glass substrates with a thickness of 100 nm. The morphological properties of the samples were identified using the Atomic Force Microscopy (AFM) apparatus in tapping mode. TEM images show amorphous structures. The phase composition of the samples was assessed using FTIR methods. The Tauc plot approach was used to examine the measured transmittance spectra in order to estimate the energy gap. Analysis of the results showed that the co-doping of DCM thin film by Znq2 influenced the structural and optical properties of the samples. To evaluate the experimental results found, theoretical calculations based on the maximum one-photon absorption (OPA) wavelengths of DCM and Znq2 have been first measured through the UV–Vis spectral technique. Then, the experimental conclusions on values for DCM and Znq2 have been compared with their corresponding simulation data procured from the time-dependent self-consistent-field (TD-SCF) computation utilizing the density functional theory (DFT) at B3LYP/6-311G(d,p) level. Besides, we have explored the first and second frontier molecular orbitals (MOs) for title compounds and their energy gaps via the DFT procedure. The calculations of maximum OPA wavelengths and the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) contributions on both molecules have also been crosschecked with the results of already published data in the literature.