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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 characteristics show that Schottky-emission (SE) type conduction mechanism is effective for MS structure, whereas Poole-Frenkel-emission (PFE) is effective for MPS structures.