In order to determine the Polyvinylpyrrolidone (PVP) effect on electrical characteristics, Au/n-Si (MS) structures with and without PVP interfacial layer were fabricated. After that their main electrical parameters were extracted from the forward and reverse biases I-V, and C/G-V measurements at room temperature. The experimental characteristics (I-V) show the MPS structure with high rectification ratio (RR=I-F/I-R at +/- 4V), shunt resistance (R-sh) and zero-bias barrier height (phi(B0)) and lower leakage current, ideality factor (n), surface states (N-ss) compared with the MS structure. RR and the reverse saturation current (I-o) for MPS are 55 times higher and 54 times lower than RR and I-o for MS, respectively. The voltage dependent n, effective barrier height (phi e) and energy dependent profile of N-ss for two types structures are acquired by considering the forward biases I-V data. They were found vary from 1.074x10(12)eV(-1)cm(-2) (at E-c-0.821eV) to 3.55x10(13)eV(-1)cm(-2) (at E-c-0.409eV) for MPS and 3.85x10(13)eV(-1)cm(-2) (at E-c-0.724eV) to 5.67x10(13)eV(-1)cm(-2) (at E-c-0.405eV) for MS structure. R-s, n and phi(B0) parameters were also found from the Cheung function as 272.4 , 6.17, and 0.964eV for MPS and 79.2 , 3.38, and 0.708eV for MS structure as second way. Some electrical parameters of the structures such as concentration of donor atoms (N-D), Fermi energy level (E-F) and BH were also found reverse bias C-2-V characteristics for 100kHz. The use of PVP polymer interlayer considerably improves the efficiency of the MS structure. The way to replace the traditional insulator interlayer concluded as; reducing the N-ss alternatively, leakage current and increase of RR, phi(B0), and R-sh, respectively.