The novel composites based on reduced graphene oxide/methylene blue/gold nanoparticles (rGO/MB/AuNPs) were synthesized by a green and easy method. This synthesis was realized through a one-step green reduction of graphene oxide and chloroauric acid by ascorbic acid, with MB as the assistant reductant and formed AuNPs as the self-catalyst. Except for electroactive substance, MB, which was firmly coated onto the surface of rGO through pi-pi stacking non-covalent interactions, also serves as the anchor for AuNPs in situ growth due to the electrostatic attraction between positively charged MB and negatively charged chloroauric ions. The characteristics of rGO/MB/AuNPs composites were investigated by various optical and electrical methods. These composites exhibit excellent electrochemical properties and promising prospects for practical application in electrochemical analysis.