Cu3Se2/Cu2Se/Cu2O hollow microspheres with Cu3Se2 as the main component have been synthesized successfully for the first time by a facile sacrificial template method at room temperature, using Cu2O microspheres as the template. The Cu3Se2/Cu2Se/Cu2O product was characterized and its formation mechanism was explored based on series of control experiments. UV-vis diffuse reflectance absorption spectrum and photoluminescence (PL) spectrum were measured to study optical properties of the Cu3Se2/Cu2Se/Cu2O hollow microspheres. The photocatalytic activities were assessed by photodegradations of three organic dye solutions in the presence of a drop of H2O2. The results show that the Cu3Se2/Cu2Se/Cu2O hollow microspheres possess high crystallinity and large ratio of hollow-sphere-diameter: wall-thickness, which can be formed at an optimal reaction condition via a dissolution-recrystallization regime. The Cu3Se2/Cu2Se/Cu2O catalyst exhibits excellent photodegradation activity to a high concentration of methyl blue solution.