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The conversion of CO2 into CO,CH4 and other hydrocarbons through solar energy can alleviate the energy shortage problem.We design a novel photocatalyst with S defects CuIn5S8@MoSe2 hollow structure.The interlayer-expanded MoSe2 can increase the adsorption of interme-diates.The unique hollow structure can improve the light utilization efficiency and the electron-holes separation.CuIn5S8 with S vacancies in bimetallic sites has high selectivity and photocatalytic reduction of CO2 activity.Therefore,S vacant CuIn5S8 confined in a few-layers MoSe2 with interlayer-expanded hollow heterostructures exhibit super performance for photocatalytic CO2 reduc-tion.After 8-h light reaction,the outputs of CO and CH4 for the 15.3 wt％ CuIn5S8@MoSe2 sample containing S vacancies (Vs) are 30.4 and 14.7 μmol·g-1,respectively.The mechanism is also investigated in detail through in situ Fourier transform infrared spectroscopy technology.