In this study, frequency and voltage dependence of dielectric constant (ε′), dielectric loss (ε″), loss tangent (tanδ), the real and imaginary parts of electric modulus (M′ and M″) and ac electrical conductivity (σac) of an Au/PVA (Bi-doped)/n-Si Schottky barrier diode have been investigated in detail by using experimental C–V and G–V measurements in the wide frequency range of 5 kHz–10 MHz and the voltage range of ±2 V at room temperature. Experimental results indicate that the values of ε′,ε″, tanδ and σac are strongly frequency and voltage dependent. It has found that the values of ε′,ε″ and tanδ decrease while the values of σac, M′ and M″ increase. It is clear that the values of M″ show a distinctive peak with a U-shape and its position shifts towards the positive-bias region with increasing frequency. Such behavior of the peak can be attributed to the particular distribution of interface states located at the Si/PVA interface and interfacial polarization. It can be concluded that the interfacial polarization and the charge at the interface can easily follow the ac signal at low frequencies.