The 50 nm thickness Zn-doped polyvinyl alcohol (PVA) was deposited on n-4H-SiC semiconductor as interlayer by electro-spinning method and so Au/Zn-doped PVA/n-4H-SiC metal-polymer-semiconductor (MPS) structure were fabricated. The real and imaginary parts of the complex dielectric constant (epsilon', epsilon ''), loss-tangent (tan 6), the real and imaginary parts of the complex electric modulus (M', M '') and ac electrical conductivity (sigma(ac)) behavior of this structure were examined using impedance spectroscopy method in a wide range of frequency (1 kHz-400 kHz) and voltage (-1 V)-(+6 V) at room temperature. The values of epsilon', epsilon '', tan delta, M', M '' and sigma(ac) are determined sensitive to the frequency and voltage in depletion and accumulation regions. The values of epsilon' and epsilon '' decrease with increasing frequency while the values of M' and sigma(ac), increase. The peak behavior in the tan delta and M '' vs. frequency curves was attributed to the dielectric relaxation processes and surface states (N-ss). The plots of ln (sigma(ac)) vs. ln (f) at enough high forward bias voltage (+6 V) have three linear regions with different slopes which correspond to low, intermediate and high frequencies, respectively. The dc conductivity is effective at low frequencies whereas the ac conductivity effective at high frequencies. According to experimental results, the surface/dipole polarizations can occur more easily occur at low frequencies and the majority of N-ss between Zn-doped PVA and n-4H-SiC contributes to the deviation of dielectric behavior of this structure.