The photocatalytic sp(3)C-sp(3)C cross-coupling between tetrahydrofuran (THF) and various alkanes was accomplished with Pt loaded titanium oxide (Pt/TiO2) photocatalysts. The cross-coupling between THF and cyclohexane was systematically studied, which revealed that the reaction followed two routes: the main course was the photooxidation of both substrates on a Pt/TiO2 photocatalyst to generate radical species followed by their successive coupling; meanwhile, the minor one was a hybrid of photocatalysis by Pt/TiO2 and thermocatalysis by Pt metal nanoparticles. The activity of the Pt catalysis was suggested to consist in the activation of an sp(3)C-H bond in THF or alkane molecules adsorbed on its surface and promote the reaction between the activated molecules and photogenerated radical species. Thus, the Pt nanoparticles on TiO2 were believed to play a bifunctional role of an electron receiver as well as a metal catalyst.