A thin (NiS-doped PVP) interface layer was spin-coated on n-Si substrate and between Au contact were prepared on the surface by the sputtering method and then their basic electrical features for example diffusion-potential (VD), doping density of donor-atoms (ND), Fermi-energy (EF), barrier-height (ΦB), and depletion layer-width (WD) were extracted reverse-bias C-2-V plots as function frequency and voltage. The voltage profile of interface/surface-states (Nss)/ relaxation-times (τ), and series resistance (Rs) were also obtained from the admittance and Nicollian-Brews method, respectively. Strongly frequency-dependent and voltage especially in both accumulation and depletion regions due to the existence of Nss, Rs, and polarization as well as (NiS-doped PVP) organic interlayer. At low frequency, the observed higher value of C and G shows that thin (NiS:PVP) interlayer can be successfully used to obtain high charges/energy storage (MPS) structure/capacitor instead of conventional insulator layer performed traditional methods. As a result, the observed important changes in electrical parameters with frequency and voltage depend on Nss, their t, Rs, organic interlayer, and interfacial or dipole polarization.