The electrochromic properties of 1,1'-dibenzyl-4.4'-bipyridinium and 1,1'-diheptyl-4,4'-bipyridinium were investigated in the presence of MBr (M = Li+, Na+, and K+). The cyclic voltammograms of these viologens showed a white-coloured state in addition to the usual violet one-electron reduction state and the colourless divalent state. Chemical analyses (FT-IR and XPS spectra) of the white film and some control experiments with different supporting electrolytes, MX (X = Cl-and I-), revealed that the viologens formed water-insoluble ion pairs with tribromide generated by the electrooxidation of monobromide to produce a white film. The film was reversibly decolourized electrochemically to the initial transparent state, providing the polyelectrochromism using the simple viologen/MBr systems. The colouration efficiencies for the violet and the white-coloured states were 170 cm(2)/C and 104 cm(2)/C, respectively. (C) 2009 Elsevier Ltd. All rights reserved.