Mesoporous-titania (TiO2) photocatalysts have been synthesized using polyethylene glycol (PEG) as a template in dilute acetic acid aqueous solution by hydrothermal process. The effect of PEG molecular weights and thermal treatment on the resultant structure and photocatalytic activity are investigated. Structural and phase compositional properties of the resultant photocatalysts are characterized by transmission electron microscopy, X-ray diffraction and nitrogen sorption analysis. When the molecular weights of PEG vary from 600 to 20,000, the particle sizes of mesoporous structure decrease from 15.1 to 13.3 nm and mean pore sizes increase from 6.9 to 10.6 nm. The chemical reactions of the formation of mesoporous-TiO2 during its synthesis have been proposed and discussed. The activities of mesoporous-TiO2 photocatalysts are evaluated and compared with Degussa P-25 using chloro-phenol as a testing compound. The reaction mechanism of photodegradation is also described on the basis of high performance liquid chromatography. (C) 2010 Elsevier Ltd. All rights reserved.