Herein, we report a facile template-free solvothermal chemical method to synthesize the hierarchical hollow CuSbS2 microspheres. The results show that the hollow microspheres with the diameter of ~800–900 nm are comprised of nanoflakes. The morphologies of CuSbS2 can be modulated rationally by adjusting the reaction parameters and the possible formation mechanism of hollow CuSbS2 microspheres with PSS (poly (sodium-p-styrenesul-fonate)) and PEG (polyethylene glycol) is studied. Moreover, the hollow CuSbS2 microspheres exhibits a photocurrent density of 0.063 mA/cm2 and an IPCE value of 32.42%, indicating that the CuSbS2 nanocrystals have potential in photoelectrochemical conversion device applications.