The main propose of this study is to investigate whether the doppant material in PVA would change the electrical characteristics of Au/PVA (X-doped) n-Si Schottky structure. Therefore, Au/PVA (Co, Zn-doped) n-Si (D1) and /PVA (Co, Ni-doped) n-Si (D2) Schottky structures were fabricated under the same condition using n-type (phosphor-doped) single crystal silicon wafer with (111) surface orientation. After the PVA/(Co-Zn) and PVA/(Co-Ni) acetates was obtained, the nanofiber film was fabricated on the silicon wafer by the use of an electrospinning technique. The results indicated that the electrical parameters of Au/PVA (x-doped) n-Si Schottky structure were significantly influenced from the doppant material in PVA. Comparative results on electrical parameters of D1 and D2 were reported in this study.