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Photocatalytic CO2 reduction into valuable fuel and chemical production has been regarded as a prospective strategy for tackling with the issues of the increasing of greenhouse gases and shortage of sustainable energy. A composite photocatalysis system employing a semiconductor enriched with oxygen vacancy and coupled with metallic cocatalyst can facilitate charge separation and transfer electrons. In this work, mesoporous TiO2 and titanium-based perovskite oxides (BaTiO3 and SrTiO3) nanoparticle assembly incorporated with abundant oxygen vacancy and copper particles have been successfully synthesized for CO2 photoreduction. As an example, the TiO2 decorated with different amounts of Cu particles has an impact on photocatalytic CO2 reduction into CH4 and CO. Particularly, the optimal TiO2/Cu-0.1 exhibits nearly 13.5 times higher CH4 yield (22.27 μmol g−1 h−1) than that of pristine TiO2 (1.65 μmol g−1 h−1). The as-obtained BaTiO3/Cu-0.1 and SrTiO3/Cu-0.1 also show enhanced CH4 ....