A new design of photocatalyst, double loading of cerium and titanium oxides on silica, was examined for the non-oxidative direct methane coupling. In the present method, both highly dispersed cerium and titanium oxide species coexisting on silica were obtained. This provided totally larger number of photoactive sites than that for the system of single metal oxide on silica. © 2006 Elsevier B.V. All rights reserved.