In order to improve and detailedly investigate the dielectric properties of polymer interfaces of Metal-Polymer-Semiconductor (MPS) structures, three types of MPS were fabricated by doping 1, 3 and 5% graphene (Gr) into the polyvinyl alcohol (PVA) interface material. Capacitance-Voltage (C-V) and Conductance-Voltage (G/omega-V) measurements were used to analyze the dielectric properties of three types of MPS. UsingC-Vand G/omega-V data, series resistance (R-s) affecting device performance and interface properties besides basic dielectric parameters of each structure such as both the real and imaginary components of complex dielectric constant (epsilon'and epsilon''), complex electrical modulus (M' and M''), loss tangent (tan delta), and ac electrical conductivity (sigma(ac)) were also calculated. The effect of graphene doping was examined for each parameter and obtained results were compared at both low (0.1 MHz) and high (1 MHz) frequencies. It was observed that epsilon and epsilon'' decreased with increasing graphene doping at both 0.1 and 1 MHz, while M' and M'' increased under same conditions. Moreover, both the M' and M'' vs V plots have two distinctive peaks between -2.0 V and 0.0 V due to a special density distribution of surface states between (Gr-PVA) and p-Si. The tan delta gradually increased with increasing graphene doping at only 0.1 MHz. As the doping ratio of graphene increases, the charge carriers in the structure generate more dipoles and create an earlier relaxation process. In other words, increasing the doping ratio helps to improve the series resistance effects in MPS structures. As a result, it was seen that the interfacial properties of MPS structures were improved by increasing the rate of graphene doping.