The photoluminescence (PL) characteristics of anatase titania particles prepared by the sol-gel method were investigated and correlated to their photocatalytic behavior with respect to the change of calcination temperature. It was found that the photoluminescence intensity measured at 77 K was gradually increased by increasing the calcination temperature due to the reduction of the internal defects which are responsible for the radiationless recombination of photoexcited electron/hole pairs. Also, the calcination temperature was found to influence the maximum peak position (X) of the photoluminescence spectra of titania. That is, a blue shift of the photoluminescence spectrum occurs as a consequence of the enlargement of the energy-gap between the lowest excited state and the ground state of titania as increasing the calcination temperature. The quenching behavior of the photoluminescence at 77 K was monitored by in situ supplying oxygen at 77 K in order to investigate what happened to the surface of titania by the calcination. The quenching intensity was monotonically increased with increasing the calcinations temperature. Based on the above results, we concluded that the calcination of titania at higher temperature produces more surface-active sites easily reacting with oxygen molecules as well as improving the crystallinity of anatase phase. Consequently, higher temperature heat treatment of anatase titania particles makes it possible to get higher photoactivity as long as no significant rutile phase is formed. (c) 2004 Elsevier B.V. All rights reserved.