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A new porous material, alveolate Cu2−xSe microsheets, was synthesized through a simple one-step solvothermal process. The surface morphology and microstructure of the as-prepared Cu2−xSe were characterized by various techniques. It was found that the as-synthesized Cu2−xSe has hierarchical porosity composed of mesopores and macropores, and rich active surfaces of {111} facets. A noteworthy visible-light-responsive photocatalytic discoloration of Rhodamine B was observed for the as-developed alveolate Cu2−xSe microsheets. The superior photocatalytic properties demonstrated by the as-synthesized Cu2−xSe are mainly attributed to the highly accessible active surfaces of the {111} facets and the wider light absorption range resulting from its narrower band gap. [ABSTRACT FROM AUTHOR]