A new class of smart complexes with reduced graphene oxide (rGO) and fluorescent amphiphilic dendrimers with triphenylamine cores, benzothiadiazole branches and poly(ethylene oxide) shells (RD) were prepared. The RD can adsorb onto rGO to enhance the dispersibility of rGO in aqueous media. The adsorbed dendrimers can be replaced by other amphiphiles, such as sodium dodecylbenzene sulfonate (SDBS) and lysophospholipid (LPC 18 : 0). This replacement was confirmed by photoluminescent spectra, X-ray photoelectron (XPS) and FT-IR spectroscopic measurements. These unique features could lead to the development of novel fluorescent turn-on biosensors based on the newly developed smart RD–rGO complexes.