© 2022, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.This study was formed by the β-naphthol orange/p-Si metal–insulator–semiconductor (MIS) structure by obtaining β-naphthol orange on the p-Si surface using the sol–gel and spin-coating techniques. FTIR, EDX, and NMR analyzes of the synthesized dye-sensitized β-naphthol orange were performed. At room temperature, the current–voltage (I–V) measurements of the Al/β-naphthol orange/p-Si MIS structure showed that the device has a high rectification ratio of 3 × 105. Series resistance values were calculated as 385 and 38 Ω by Norde and Cheung methods, respectively. It was determined that the interface state density of the device was at the level of 1013 eV−1 cm−2 and increased exponentially from the middle of the bandgap to the upper edge of the valence band. Frequency-dependent capacitance–voltage (C–V) measurements at room temperature showed that the interface state densities in the device are effective in determining device parameters.