The novel work for this study is to make new films for the pure and doped PVC with organosilane; thus, it used organosilane moieties (25 mg) mixed with poly(vinyl chloride) (5 g). Thus drop-casting procedure was utilized to make these thin films. The pure PVC and PVC-organosilane (Si-L-NO 2 /PVC called SI and Si-L-Br called SII) optical properties were studied under the wavelength range from (250 to 1300 nm) using diffusive reflectance equipment. The optical properties like absorption increased up to (87–95%), while reflectance and transmittance decrease when added organosilane molecules. Furthermore, the dielectric constant (real and imaginary) and optical conductivity enhanced, respectively. On the other hand, Urbach energy increases when adding organosilane to PVC structure from 7.7011 to 14.146 eV; furthermore, skin depth, refractive index, and optical density were figured. The energy gap is reduced from 4 to 2.3 eV for the direct transition and from 3.4 to 1.6 eV for the indirect transition. SEM analysis was implemented over thin films of pure PVC and PVC-organosilane to see the morphology of these surfaces. The AFM analysis was utilized to exhibit the topography of the surfaces, thereby finding the surface roughness and the root-mean-square of the surface for these thin films. The improvement for these thin films is used in many applications such as absorption of the light when used as a coating in flat plate collector, and declines the reflectance in radars, strength external applications such as doors, windows, and the dielectric material in electronic devices.