The application of organic semiconductors particularly Poly(3,4-ethylene dioxythiophene (PEDOT) for microelectronics has attracted great interest from academia and the industry. PEDOT exhibits attractive features such as high electrical conductivity, fast redox potential, and stability in ambient temperature. When combined with 2D nanomaterials such as graphene, the resulting PEDOT-based nanocomposites display enhanced properties owing to the synergistic interaction of the host matrix and the filler. With the growing research in this area of study, little is known about the adsorption mechanism of PEDOT with the surface of graphene. Therefore, we employ material modeling to gain an understanding of the adsorption of PEDOT on the surface of graphene nanosheet. Monte Carlo simulation was performed to determine the various configuration of low-energy adsorption sites for the adsorbate on the graphene surface. Then the electronic structure of the adsorbate was determined using DFT. In addition, the root mean square distance of the atoms in the molecule of PEDOT repeating unit from their common center of mass to the surface of the nanosheet, the binding energy, charge density at the interface, and band structure of the nanofilm were investigated. Key Words: Graphene, Monte Carlo, DFT, PEDOT, Polymer Nanocomposite