The growth of silicate tungsten bronzes on aluminum by plasma electrolytic oxidation in 12-tungstosilicic acid is experimentally investigated and discussed. Real time imaging and optical emission spectroscopy characterization of plasma electrolytic oxidation show that spatial density of microdischarges is the highest in the early stage of the process, while the percentage of oxide coating area covered by active discharge sites decreases slowly with time. Emission spectrum of microdischarges has several intensive band peaks originating either from aluminum electrode or from the electrolyte. Surface roughness of obtained oxide coatings increases with prolonged time of plasma electrolytic oxidation, as their microhardness decreases. Raman spectroscopy and energy dispersive X-ray spectroscopy are employed to confirm that the outer layer of oxide coatings formed during the plasma electrolytic oxidation process is silicate tungsten bronzes. (C) 2011 Elsevier B. V. All rights reserved.