2,4,6-Triphenylpyrylium (TP+), an electron acceptor, has been included inside the channels of two ordered mesoporous titania (mpTiO2). MpTiO2 contain anatase nanoparticles (3–5 nm) templated by cetyltrimethylammonium and differ by the presence or absence of silica domains as binders of the structure. UV irradiation of T–mpTiO2 gives rise to a strong EPR signal. This behaviour was not observed for related materials in which TP+ was included inside the channels of MCM-41 or the cavities of zeolite Y. Also, transient spectroscopy shows remarkable differences between TP+ included in mpTiO2 (charge separation) and in porous silicates (triplet excited state). Based on EPR and laser flash spectroscopic evidence, the occurrence of photo-induced electron transfer from TiO2 as the donor to TP+ as the acceptor leading to a long-lived (minutes at room temperature) charge separated state is proposed.