A novel supramolecular photoswitch containing bisthienylethene-pyridine (BTEPy) and carboxyl attached tetrathiafluvalene (TTF-COOH) was constructed via intermolecular hydrogen bond. FT-IR spectra, XPS characterizations, H-1 NMR and theoretical calculation were carried out to verify the formation of the intermolecular hydrogen bond. The supramolecular self-assemblies BTEPy 2TTF show good photo-chromic properties. A molecular switch with UV/vis light as inputs and electrochemical signals as outputs was obtained. (c) 2008 Elsevier B.V. All rights reserved.