In this study, the frequency/voltage dependence of the dielectric constant (epsilon '), dielectric loss (epsilon ''), real/imaginary components of the complex electric modulus (M ', M ''), tangent loss (tan delta), ac electrical conductivity (sigma(ac)), real and the imaginary parts of the complex impedance (Z*), phase angle (theta) between resistance current, and capacitive current of the Al/(Coumarin: PVA)/p-Si structures were investigated using C/G-V-f measurements in wide range of frequency (10 kHz-1 MHz) and voltage (+/- 5 V) by 0.05 V steps. These parameters showed strong dependence on frequency and voltage due to the existence of surface states (N-ss), their life/relaxation time (tau), series resistance (R-s), and polarization processes. epsilon ' and epsilon '' values were found to be high at lower frequencies and this was explained by the fact that the interfacial dipoles have enough time to orient themselves in the direction of the signal and thus N-ss can easily follow it. M '-V and M ''-V plots both have a distinctive peak at depletion region and peak position shifts toward accumulation region with increasing frequency due to restructuring and reordering of N-ss under electric field and polarization. ln(sigma)-ln(f) plots for accumulation region show two linear parts with different slopes, and this provides an evidence to the existence of two different conduction mechanisms which correspond to intermediate and high frequency regions. The strong dispersion in epsilon ' and epsilon '' at lower frequencies was attributed to the N-ss, Maxwell-Wagner-type polarizations.