In this study, Au/n-Si structures with PVP polymer interlayer were fabricated and characterized using capacitance/conductance-voltage-frequency (C/G-V-f) measurements. Obtained electrical parameters were found to be sensitive to frequency due to polymer interlayer, changes of traps/states (D-it/N-ss) level, interfacial/dipole polarization. The dispersion in C and G in depletion region is due toN(ss)/polarization, while the dispersion in accumulation region is due to interlayer/series resistance (R-s). The voltage-dependent profiles ofN(ss)andR(s)were derived using the methods of low-high frequency capacitance/Hill-Coleman and Nicollian-Brews, respectively. The width of depletion layer (W-d) and barrier height (phi(B)) values increase with increasing frequency almost linearly. On the other hand,R(s)decreases with increasing frequency whereas the maximum electric field (E-m) exhibits opposite behavior. The high frequency C/G-V plots were corrected to reveal theR(s)effect on them. The experimental results indicate that the growth of PVP interlayer by spin coating at the Au/n-Si interface yields a preferable and suitable device compared to devices with conventional insulating interlayer due to some advantages of polymer interlayers such as low-cost/weight, flexibility, and easy grown processes.