In the paper, graphene oxide (GO) and two kinds of styrenic resins, poly[styrene--(ethylene--butylene)--styrene] (SEBS) and maleic anhydride (MA) grafted SEBS (MA--SEBS), were utilized to explore the interfacial interaction of carbon-based materials and block copolymers as layer-by-layer (LBL) assembly films. The details of the interlayer interaction of the two kinds of composite films were investigated through the analysis of the mechanical properties and internal structure of the composites. For the SEBS/GO composite film, the "interlock" structure tended to form between the GO sheets and SEBS resin, and the physical "interlocking effect" could make full use of the excellent mechanical properties of GO nanosheets. As a result, both failure strength and elongation at break of the SEBS/GO composite film were enhanced by 50 and 25%, respectively. On the other hand, some different structures were found in the MA--SEBS/GO composite film, where the GO sheets stacked onto the resin closely because of the chemical interaction between them and no obvious "interlocks" was found within the interface, and the chemical interface interaction was strong enough to prevent the slide of GO nanosheets under tension after the graphene sheets were highly oxidized, so the mechanical properties of the MA--SEBS/GO composite film could be also enhanced. Based on an overall consideration of the research results of these LBL assembled composites, choosing more perfect materials and structures is needed, which should use physical and chemical interfacial interactions more efficiently, to obtain better mechanical properties of inorganic carbon-organic resin composites.