Piperonal (heliotropine or 3,4-methylenedioxybenzaldehyde) has been synthesized by oxidizing piperonyl alcohol in aqueous UV-irradiated TiO2 suspensions. This compound was identified by GC-MS chromatography,H-1 NMR and melting point determination. The other products of the photoprocess were 1,3-bis(3,4-(methylenedioxy)benzyl) ether (found in traces) and CO2, derived from the parallel pathway of photo-mineralization. Commercial and home-prepared TiO2 samples have been tested and the best selectivity (ca. 35%) was obtained by using the home-prepared ones. The reported green process allows to obtain an added value product (piperonal), upon partial oxidation of a cheap reagent. (C) 2013 Elsevier B.V. All rights reserved.