In this paper, the polyvinyl pyrrolidine (PVP) polymer layer doped by barium titanate (BaTiO3) nanostructures has been prepared as an interfacial layer to fabricate a metal-semiconductor-metal (MPS) diode. The inserted layer in the metal-semiconductor (MS) structure can be changed its dielectric properties which have been studied in this work. In addition, the frequency-dependent impedance measurements are performed at 1.5 V in frequency range 100 Hz-1 MHz. The variations of the dielectric constant (epsilon('))/loss (epsilon('')), electrical modules, and ac electrical conductivity sigma(ac) of them are investigated. It is found that the use of interfacial layer increases dielectric constant of the MPS five times more than MS. Also, PVP: BaTiO3 interlayer increases the electrical conductivity by decreasing the interfacial polarization. The results show that the conduction mechanisms are charge carrier's interaction and trap states at the low/intermediate frequency and well-localized relaxation process at the high frequency. Therefore, PVP: BaTiO3 interlayer can be a suitable alternative replacement of intrinsic interlayer for utilization in the nanoscale electronic and optoelectronic devices and circuits.