Poly(3,4-ethylenedioxythiophene) (PEDOT) has been electrochemically polymerized from 3,4-ethylenedioxythiophene (EDOT) monomers through a vertically oriented mesoporous silica matrix previously formed on FTO electrodes. The mesoporous silica thin films with pore channels of 3 nm in diameter, closely packed in a hexagonal arrangement, were obtained by electrochemically-assisted self-assembly (EASA). The mesoporous silica/PEDOT films were characterized by SEM and TEM microscopy and by cyclic voltammety. They were also used to construct electrochromic devices (ECDs), which were fully characterized for switching speed, coloration efficiencies, and cycling and voltammetric responses. (C) 2016 Elsevier B.V. All rights reserved.