Water-soluble sulfonated monomer based on 3,4-propylenedioxythiophene (ProDOT-sultone) was synthesized and characterized for the first time via the O-alkylation of the corresponding unreactive beta,beta-disubstituted hydroxyl group with propane sultone in the presence of a catalytic amount of 1,4-diazabicyclo[2.2.2]octane (DABCO). This new monomer was oxidatively polymerized to produce regioregular water-soluble conjugated anionic polyelectrolyte, which was then used for the fabrication of solid-state electrochromic devices using the layer-by-layer (LbL) deposition method. These solid-state devices were found to exhibit better electrochromic properties in terms of color contrast, switching time, coloration efficiency (CE), surface control electroactivity, and conductivity in thin films compared with the corresponding water-soluble regiorandom 3,4-ethylenedioxythiophene (EDOT) derivative. For the 40 and 80 bilayer solid-state electrochromic devices, the electrochemical contrast was observed to be 31 and 40% at 570 nm with fast solid-state switching times of 100 and 220 ins, respectively, indicating faster movement of the ions in and out of the films. Furthermore, the CE was found to be as high as 250 cm(2)/C for the 80 bilayer device and was independent of the device thickness, indicating the full accessibility of all of the ionic sites, even in thicker films. Four-point probe conductivity of the LbL and in situ conductivity of solution cast films were found to be in the range of 10(-4) and 10(-3) S/cm, respectively.