Photoelectrochemical synthesis of TiO2/CdX/PEDOT [X: S, Se; PEDOT = poly(3,4-ethylenedioxythiophene)] ternary hybrids was carried out by exploiting the semiconductor (SC) nature of both the oxide and the chalcogenide component. To this end, TiO2 nanotube arrays were initially electrosynthesized on titanium foils by anodization in fluoride-containing aqueous media. CdS and CdSe quantum dots were subsequently deposited on the nanotubes using successive ionic layer adsorption and reaction (SILAR). The conjugated polymer, PEDOT, was then grafted using photoelectrochemical excitation of the SC matrix and potentiodynamic deposition, to ultimately afford the ternary hybrid architecture. The morphology, structural properties, and chemical composition of these assemblies were evaluated by scanning electron microscopy, diffuse reflectance UV-Vis spectrophotometry, and Raman spectroscopy, while their electroactivity was evaluated by cyclic voltammetry. Photoelectrochemical deposition of the conducting polymer was carried out both through selective excitation of the chalcogenide sensitizer and the collective photoexcitation of the two SC components. Two precursor molecules, namely, EDOT or bisEDOT were compared and contrasted in terms of their relative proclivity to oligomer/polymer formation. The use of UV or visible spectral wavelength components allowed for discrimination between the various polymer formation and SC photoexcitation pathways. (C) 2014 Elsevier Ltd. All rights reserved.