<p>Optical materials organic in nature are leading materials exhibiting semiconducting properties which is a trend of present technology for optical and electronic applications. Active organic materials of Schiff bases are of vital importance in terms of their molecular properties, band gap, refractive index, and dielectric operated at room temperature compared to inorganic materials at elevated temperatures during synthesis. The article focuses on the development of thin films with green synthesis of Schiff base of 4-hydroxy benzaldehydes with different anilines for optoelectronic applications. The formation of the Schiff base compounds was confirmed with spectroscopic methods showing shifts in wavenumbers in infrared spectra, transition with optical band gap in ultraviolet spectra, and chemical environment with chemical shifts using proton NMR. Powdered XRD provided information of structure, composition, and crystalline proximity of the synthesized Schiff base compounds. Optical properties such as refractive index and dielectric constant were attributed with spectroscopic ellipsometer. Computational studies were performed using the Gaussian 16 package with the B3LYP method basis set 6–311 +  + ** for all molecular compounds to confirm the molecular structures, optimized geometry, and electronic and optical properties. The insights of these properties are best visualized in terms of quantum mechanical descriptors responsible for changes in electron density. Studies of synthesized Schiff base compounds with nitro groups find widespread use in variety of applications and can be employed as excellent organic semiconducting material with an energy gap of 3.08&#xa0;eV, refractive index of 2.074, and dielectric constant of 4.303.</p>