In the present study, thin films of PVP-SiO2-TMSPM (polyvinylpyrrolidone-silicon dioxide- 3-trimethoxysilyl propyl metacrylate) were deposited on p-type Si (111) substrates using spin coating technique. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and energy dispersive X-ray spectrometry (EDS) were applied to investigate the chemical bonds and structural properties of the samples. Morphology of the hybrid thin films was studied using atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. The frequency dependence of dielectric properties such as dielectric constant (ε′), dielectric loss (ε″), loss tangent (tan δ) as well as the real component of electric modulus (M′), imaginary component of electric modulus (M″), and AC electrical conductivity (σAC) was studied in Al/PVP-SiO2-TMSPM/PSi used as a metal-polymer-semiconductor (MPS) device. Analysis of dielectric relaxation behavior was performed in the frequency range of 0.1 KHz to 1 MHz. In the frequency range of 1 KHz to 1 MHz, the σAC data were varied from 6.35 × 10−6 to 9.02 × 10−6 for the sample with 0.15 wt ratios of TMSPM and equivalent values of both PVP and SiO2. The dielectric, modulus, and AC conductivity analyses were considered the useful factors to detect the effects of the capacitance, ionic conductivity, and dielectric relaxation process.