A novel hybrid consisting of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HOPTS) and graphene oxide (GO) was firstly synthesized as GO@HOPTS, which was confirmed to exhibit green luminescence emission. Then, GO@HOPTS and heteropolyanion NaP5W30O11014-(P5W30) were utilized to fabricate the composite films {(PDDA/P5W30)(5)/I(PDDA/P5W30)(5)/PDDA/GO@HOPTS](15)/(PDDA/P5W30)(5)} on quartz substrate and conductive ITO-coated glass electrode by the layer-by-layer (LBL) assembly deposition technique based on the electrostatic attraction of oppositely charged species. The composite films were characterized by cyclic voltammetry (CV), fluorescence spectroscopy, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The electrofluorochromic performance of the composite film was investigated by in situ UV-vis spectroelectrochemical and fluorescence spectroelectrochemical measurements under electrochemical modulation. The results indicate that the composite film displays not only green luminescence emission but also reversible green luminescence switching behaviors manipulated by the redox process of P5W30 via the energy transfer between the green luminescence component HOPTS and electroreduced species of P5W30. (C) 2015 Elsevier B.V. All rights reserved.