In this work, a feasible solvothermal strategy to the preparation of double-shelled Cu2O hollow microspheres is described. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of the as synthesized precipitate revealed that they were hierarchical structures composed by nanoparticles. Moreover, the formation mechanism of double shell Cu2O hollow microsphere was studied. Gas sensing devices were fabricated using the Cu2O suspension by coating, and their sensing properties were investigated for response to various gases. The double shell Cu2O hollow microspheres sensors showed good selectivity to n-propanol (C3H8O) at 187 degrees C, a better linear range from 10 to 100 ppm, good repeatability and long-term stability. The excellent sensing performance of sensors to n-propanol could be ascribed to the hierarchical structures with a large specific surface area.