In this work, a new copolymer synthesis of Poly(acetoxystyrene-co-glycidylmethacrylate) (P[AOS-co-GMA]) by free radical polymerization (FRP) method is reported. The polymer composites (P[AOS-co-GMA]/graphene), containing different amounts of graphene, were prepared by the solution casting technique. Composites of Poly(acetoxystyrene-co-glycidylmethacrylate) loaded with 2.03 mass%, 5.00 mass%, 7.97 mass%, and 10 mass% graphene. The structure of AOS-GMA systems was characterized by fourier transform infrared, 1 H-NMR and scanning electron microscopy. Thermal features were evaluated by the thermogravimetric analysis and differential scanning calorimetry. The aim of this study is to optimize the ε 0 (dielectric constant) and ε 00 (dielectric loss factor) of pure polymer and graphene-doped (2.03-5-7.97-10 mass%) P(AOS-co-GMA) composite using response surface methodology. For optimization of the process and creation of the mathematical model, the central composite design package was used. The significance of the process parameters in the model was evaluated by analysis of variance (ANOVA) research. The effects of process parameters, frequency (Hz), voltage (V), and graphene ratio (mass%) on ε 0 and ε 00 were examined at ambient temperature. The maximum ε 00 value (8.01) was reached at around the 699 Hz frequency and at 11.43 V voltage at the graphene content of 9.82 mass%. The model estimated the maximum value of the ε 00 (0.08) when the frequency was set at 51.20, the voltage was fixed at 1.16 and the graphene content was fixed at 9.97 wt%. The ANOVA results showed that frequency and graphene content were the main model parameters and had a remarkable effect on the dielectric properties. This article presents the development of a new polymeric composite and optimize effect of process parameters, such as frequency (A), voltage (B) and amount of graphene (C).