Luminescent materials with stimuli-responsive behavior have good prospects for application in displays, sensors, and other fields. In this research, a type of luminescent supramolecular polymer was fabricated, via hydrogen bonding, that shows stimuli-responsive behavior with different types of acid. Firstly, the acceptor material luminogen (4,4′-dibutanoxy tetraphenylethylene)-1-pyridine (PTPEC₄) is synthesized. Then, the PTPEC₄ is used to prepare luminescent supramolecular polymer PVA(PTPEC₄)_x by complexing the donor material poly(vinyl alcohol) (PVA) with different amounts of PTPEC₄. The PVA(PTPEC₄)_x exhibits a lamellar structure at x ≥ 0.6, whereas a crystalline structure forms with x ≤ 0.4. Because of the protonation effect of the pyridine group in PTPEC₄, PVA(PTPEC₄)_x not only exhibits solid-state emission behavior but also presents multicolor luminescence switching under different acid vapors. Moreover, because of the existence of the hydrogen bonds, PVA(PTPEC₄)_1.0 shows a reversible, spontaneous fluorescence switch under acid vapor with a pK_a > 5.25. If the sample is fumed with acid vapor with pK_a < 5.25, PVA(PTPEC₄)_1.0 only exhibits a larger luminescence red shift but cannot recover unless the sample is treated with triethylamine vapor. Furthermore, a rewritable paper with tunable multicolor emission and high contrast is prepared based on the fluorescence response and recovery behavior, which may be applied in optical memory systems.