Hybrid nanopaper-like thin films with a graphene oxide (GO) layer sandwiched by two functionalized graphene (GP-SO3H) layers were successfully prepared from oxidized graphene and benzene sulfonic modified reduced graphene by filtering dispersed GP-SO3H and GO solution layer-by-layer. In order to modify the surface of graphene particles with sulfonic acid groups, The expanded graphite was first oxidized into graphite oxide through Staudenmaier’s method, and then exfoliated into individual single-layer graphene oxide sheets under mild ultra-sound. The resultant graphene oxide was then undergo partial reduction with NaBH4, group attachment with diazonium compounds, and full reduction with hydrazine to get the surface modified graphene, GP-SO3H. The graphene-graphene oxide-graphene nanopaper (GP-GO-GP) hybrid nanopaper showed excellent combination of high mechanic strength of 108 MPa without annealing, and good electrical conductivity as high as 2.3 x104 S/m, leading to desirable electromagnetic interference (EMI) shielding of 33-48 db, from the GP-SO3H layers, and superior hydrogen and carbon dioxide gas diffusion barrier provided by the GO layer. The nanopapers can be readily coated onto polymer substrates by either thermal lamination with polyester films or in-mold coating type injection molding process. The industrial applications of the hybrid nanopaper including 1) coating of the gas tank, e.g. hydrogen or natural gas tank to eliminate the risk of gas escape, and 2) food package that requires perfect gas barrier property against oxygen permeation.