This article presents a combination strategy of electrodeposition and a layer-by-layer assembly to fabricate functional composite films with luminescence switching behavior. Firstly, a novel green luminescence film consisting of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HOPTS) was first obtained on ITO by a facile electrodeposition method. Then, the multilayer films containing different layers of tungstophosphate K12.5Na1.5[NaP5W30O110]·15H2O (P5W30) were further fabricated on the green luminescence film to form the composite films [(HOPTS)50/(PDDA/P5W30)n] (n = 10, film 1; n = 27, film 2; n = 57, film 3). Cyclic voltammetry and fluorescence spectroscopy were used to characterize the electrochemical activity of P5W30 and the luminescence property of HOPTS in the composite films, respectively. Lastly, in situ UV-Vis spectroelectrochemical and fluorescence spectroelectrochemical measurements were applied to investigate the luminescence switching behaviors of the composite films controlled by the electrochromism component of P5W30 upon electrochemical modulation. In summary, the investigation results revealed that the electrodeposition method is convenient and rapid, and thus-prepared composite films showed improved luminescence switching performance in terms of switching process, activation cycles, coloration efficiency, and bleached-state transparency as well as good stability, wide voltage range and good reversibility. Therefore, the present study offers a new fabrication route for the multifunctional composite films through an effective combination of electrodeposition and layer-by-layer assembly technique.