In this work, Au/n-Si (MS) structures with and without (Fe2O4-doped PVP) interlayer were prepared with the same conditions to see effects of organic layer on the electrical characteristics and conduction mechanisms. For this aim, I-V and Z-V measurements of them were carried out at room temperature. The saturation current (I-s), ideality factor (n), barrier height (phi(B)(I-V)), series (R-s) and shunt (R-sh) resistances, and rectifying rate (RR = I-F/I-R) of them were extracted from the I-V data as 2.90 x 10(-8) A, 1.699, 0.741 eV, 1.58 k ohm, 25.7 M ohm, 1.45 x 10(4) for MS and 2.30 x 10(-9) A, 1.634, 0.806 eV, 1.17 k ohm, 103 M ohm, 9.01 x 10(4) for MPS, respectively. The values of interface states (N-ss) were also extracted from the I-V data at forward bias by considering voltage dependent BH and n, and it is found that they increase from the mid-gap of semiconductor towards the conductance band. The values of doping atoms (N-D), Fermi-energy (E-F), and (phi(B)(C-V)) were also acquired from the C-2-V plots at reverse bias as 9.08 x 10(14) cm(-3), 0.258 eV, 0.914 eV for MS and 7.650 x 10(14) cm(-3), 0.263 eV, 0.981 eV, for MPS structure, respectively. It is clear that the (Fe2O4-PVP) interlayer leads to decreases in R-s, N-ss, leakage current and increase in rectifying rate (RR), R-sh and BH, so that it can used in place of the conventional oxide or insulator layer.