We show herein that Pt-modified carbon-titanium dioxide cathode nanocomposite matrices (designated hereafter as Pt/C-TiO2), prepared by heterogeneous photocatalysis, afford facile electrocatalytic reduction of carbon dioxide to methanol and isopropanol. Pyridinium cation was used as a solution co-catalyst in this study. The electrocatalytic activity of the new-generation Pt/C-TiO2 cathodes was quantitatively mapped by the combined use of rotating disk electrode voltammetry along with gas chromatography assay of the reduction products in solution. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.008201esl] All rights reserved.