© 2020, Springer-Verlag GmbH Germany, part of Springer Nature.For the investigation of the influence of (PVP: Zn-TeO2) interphase layer on the electrophysical parameters, Al/p-Si structures with/without (PVP: Zn-TeO2) interlayer grown by spin-coating technique and then these factors were studied by I–V and Z–f measurements. First, the Field Emission Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), Energy Dispersive X-ray Spectroscopy (EDS), and UV–Vis analyses techniques were performed to investigate the morphology, purity determination, and the optical properties of the nanostructures, respectively. Second, I–V measurements and Z–f were performed at ± 3 and 1.5 V (at 100 Hz–1 MHz), respectively. The values of ideality factor (n), barrier height (BH:ΦB), and series resistance (Rs) of them were obtained using various methods such as thermionic emission, Cheung’s and Norde functions and compared. The energy dependence of surface states (Nss) were extracted from the forward bias I–V measurements by assuming the voltage dependence of BH and n. The frequency-dependence profiles of dielectric constant (ε′)/loss (ε″), and ac electrical conductivity (σac) were extracted from the Z–f measurements. Experimental results show that (PVP: Zn-TeO2) interlayer leads to an increase in the ε′, ε″, BH, Rsh, and decrease in Nss. Therefore, Al/(PVP: Zn-TeO2)/p-Si structures can be used as an electronic part in nanoscale instead of MS structures.