Individually dispersed graphene colloid is prepared using cationic dye rhodamine B (RhB) as a non-covalent modifier. Characterizations by UV-vis, photoluminescence and Raman, the graphene-RhB interactions are shown to be cation-pi and pi-pi. Subsequently, the obtained graphene is incorporated into polyvinyl alcohol (PVA) to fabricate PVA/graphene composites by simple solution casting. On addition of 1.0 wt% graphene, the tensile strength and tensile modulus are increased by 178% and 139%, respectively. Interestingly, the strain of the composites is greatly maintained, which is related to the uniqueness interfacial structure and morphology of the composites. This work provides a promising methodology to fabricate high performance graphene-based composites with superior strength and ductility by simultaneously combining the reinforcement of graphene sheets and the uniqueness interfacial structure. (C) 2011 Elsevier Ltd. All rights reserved.