Semiconductor oxides with hierarchically hollow architecture can provide significant advantages as sensing materials for gas sensors by facilitating the diffusion of target gases. Herein, we develop a facile template-free solvothermal strategy combined with the subsequent thermal treatment process toward the successful synthesis of novel ZnFe2O4 hollow flower-like microspheres. The images of electron microscopy unambiguously indicated that the ZnFe2O4 nanosheets with thickness of around 20 nm assembled hierarchically to form the unique flower-like architecture. As a proof-of-concept demonstration of the function, the as-prepared product was utilized as sensing material for gas sensor. Significantly, in virtue of the porous shell structure, hollow interior, and large surface area, ZnFe2O4 hierarchical microspheres exhibited high response, excellent cyclability, and long-term stability to acetone at the operating temperature of 215 °C.