In this study, we present a facile method of fabricating graphene oxide (GO) films on the surface of polyimide (PI) via layer-by-layer (LBL) assembly of charged GO. The positively charged amino-phenyl functionalized GO (APGO) is alternatively complexed with the negatively charged GO through an electrostatic LBL assembly process. Furthermore, we investigated the water vapor transmission rate and oxygen transmission rate of the prepared (reduced GO [rGO]/rAPGO)10 deposited PI film (rGO/rAPGO/PI) and pure PI film. The water vapor transmission rate of the GO and APGO-coated PI composite film was increased due to the intrinsically hydrophilic property of the charged composite films. However, the oxygen transmission rate was decreased from 220 to 78 cm3/m2·day·atm, due to the barrier effect of the graphene films on the PI surface. Since the proposed method allows for large-scale production of graphene films, it is considered to have potential for utilization in various applications.