In this study, both the Au/(pure-PVA)/n-Si (MPS-1) and Au/(CdTe:PVA)/n-Si (MPS-2) type Schottky diodes (SDs) were fabricated onto the same n-Si wafer in same conditions. After that, their electrical parameters were obtained from the current–voltage (I–V) and capacitance–voltage (C–V) measurements and compared to each other to determine the effect (CdTe:PVA) interlayer on the performance of MPS type SD. The saturation current (Is), ideality factor (n), rectification ratio (RR = Ifor./Irev.), zero-bias barrier height (ΦBo), and series/shunt resistances (Rs, Rsh) were derived utilizing I–V data. The values of Io, n, and ΦBo were found as 9.13 × 10–7 A, 11.07, 0.63 eV for MPS1 and 1.54 × 10–10 A, 3.97, 0.85 eV for MPS2, respectively. The C−2–V graphs were drawn for 0.7 MHz to obtain the doping concentration of donor atoms (ND), Fermi energy (EF), BH/(ΦB(C–V)), depletion layer width (WD), and maximum electric field (Em). The Nss − (Ec − Ess) profile for two SDs was produced from the I–V data by considering the voltage dependence of n and BH. The values of surface states (Nss) were changed between 4.8 × 1013 and 1.7 × 1014 eV−1 cm−2 for MPS1 and 5 × 1012 and 1.15 × 1013 eV−1 cm−2 for MPS2, respectively. All experimental results show that the (CdTe:PVA) interlayer significantly improved the quality of the MS type SDs rather than (pure-PVA) in terms of lower values of leakage/saturation current, n, Nss, and higher RR, BH, and Rsh when compared (pure-PVA) interlayer. The (CdTe:PVA) interlayer may be used instead of the conventional interlayer in the future.