The effects of polyvinylchloride (PVC) and samarium oxide-polyvinylchloride (PVC: Sm2O3) polymer interlayers on the electrical characteristics in detail. The fabricated reference sample Au/n-Si, Au/PVC/n-Si, and Au/(PVC: Sm2O3)/n-Si were named as Metal-Semiconductor (MS), Metal-Polymer-Semiconductor (MPS1), and MPS2 structure, respectively. The procedure of providing Sm2O3 is also described in detail. XRD, FE-SEM), EDX, and UV-vis spectroscopy, have been applied to study the mean crystalline structure, morphology, elemental characterization, and optical features of the provided Sm2O3. After structural analysis, the I-V features were performed in the wide range voltage (+/- 3.5 V), and then, the basic electronic parameters of these structures were extracted from various techniques and compared with each other. Experimental results show that (PVC: Sm2O3) leads to an increase of barrier-height (BH), rectifying-rate shunt-resistance (R-sh ), and decrease of ideality-factor (n), surface-states (N-ss ). The RR of the MPS2 structure was found 117 times higher than the MS structure. The energy-dependent profile of N (ss) was also obtained from the forward bias I-V data by considering voltage-dependent n and BH. The plots reverse-bias IR-VR0.5 characteristics show that Schottky-emission (SE) type conduction mechanism is effective for MS structure, whereas Poole-Frenkel-emission (PFE) is effective for MPS structures.