In order to see an interlayer on the electrical parameters and conduction mechanisms (CMs), both the metal-semiconductor (MS) and Au/(MgO-PVP)/n-Si Schottky diodes (SDs) were grown onto the same wafer with < 100 & rang; orientation and 350 mu m thickness. Next, their electrical parameters, such as the ideality factor (n), barrier height (phi(B)), and series resistances (R-s) were obtained from the current-voltage (I-V) measurements using thermionic emissions, theory, and Cheung and Norde functions and compared. The energy-dependent distribution of interface traps/states (D-it/N-ss) of these two structures were extracted from theI-Vdata in the forward biases by considering the voltage-dependentnand phi(B). Experimental results confirmed that theN(ss)for a metal-polymer-semiconductor is considerably lower than for an MS, and it increases from the mid-gap towards the edge of the conduction band (E-c). The ln(I)-ln(V) curves have three straight lines which correspond to low, moderate, and high biases, and CM is governed by ohmic, trap/space-charge-limited current, respectively. When comparing these results, MgO-PVP leads to considerably improving the performance of the MS in respect of lower values ofN(ss),R-s, the reverse saturation current (I-o) and higher values of the rectifying rate, phi(B), and the shunt resistance (R-sh), and hence it can be successfully used instead of a traditional insulator interlayer.