The admittance measurements of the fabricated Au/(%1Ni-PVA)/n-Si (MPS) structure were performed within the frequency range of 5 kHz-5 MHz and voltage range of +/- 3 V with 50 mV steps. C and G values were found to be strong functions of frequency & voltage. These parameters took high values at lower-frequencies and it was associated with the surface-states (N-ss) located at Au/(%1Ni-PVA) interface and surface/dipole polarization. The existence of N-ss also led to other effects such as peak behavior at distinct voltages for the plot of Gp/omega-log(f). Corrected values of the measured C and G were obtained by eliminating the effects of series resistance (R-S) on them. As a result of this correction, the corrected value of C increases with increasing voltage at accumulation region whereas G(C) decreases and shows a distinctive peak. The basic electrical parameters calculated from the reverse bias C-2-V plots were also found to be strong functions of frequency and frequency-dependent coefficient of Os was found as 14.1 x 10(-3)eV. Obtained low values of N-ss (approximate to 10(12) eV(-1) cm(-2)) were attributed to the passivation effects of (%1Ni-PVA) interlayer and hence it can be successfully used as interlayer material that is alternative to the conventional oxides regarding the enhancements in device parameters.