Two types of Schottky diodes, with and without PVA (Ni-doped) layer, were fabricated to investigate whether or not the PVA (Ni-doped) layer is effective on some electrical parameters such as ideality factor n, barrier height [Formula: see text] , series resistance Rs, and interface state density NSS. PVA (Ni-doped) microdrops film was deposited on n-type silicon substrate. SDs with and without PVA (Ni-doped) layer, namely MPS and MS diodes, respectively, were investigated by current–voltage ( I–V) measurements at room temperature. Also, series resistance calculations have been performed using Cheung method. The values of n and Rs obtained for MPS are found higher compared to those of MS. This is attributed to the particular distribution of NSS, and inhomogeneity of barrier height and interfacial layer at metal/semiconductor (M/S) interface. Au/PVA(Ni-doped)/n-Si diode (MPS) exhibits a photovoltaic behavior with an open circuit voltage Voc 0.42 V and short-circuit current ISC 33.2 µA under 100 mW/cm2 illumination intensity. The obtained photovoltaic results indicate that the MPS diode can be used as an efficient material for applications in optoelectronic applications such as solar cells and photodiode devices.