In this study, the temperature-dependent mean density of interface states ðN SS Þ and series resistance ðR S Þ profiles of Au/PVA (Ni,Zn-doped)/n-Si (111) structures are determined using current-voltage (IÀV) and admittance spectroscopy [capacitance-voltage (C-V) and conductance-voltage G/x-V] methods. The other main electronic parameters such as zero-bias barrier height ðU B0 Þ, ideality factor (n), and doping concentration (N D ) are also obtained as a function of temperature. Experimental results show that the values of U B0 , n, R S , and N SS are strongly temperature dependent. The values of U B0 and R S increase with increasing temperature, while those of n and N SS decrease. The C-V plots of Au/PVA (Ni,Zn-doped)/n-Si(111) structures exhibit anomalous peaks in forward bias (depletion region) at each temperature, and peak positions shift towards negative bias with increasing temperature. The peak value of C has been found to be strongly dependent on N SS , R S , and temperature. The experimental data confirm that the values of N SS , R S , temperature, and the thickness and composition of the interfacial polymer layer are important factors that influence the main electrical parameters of the device.