A template-free hydrothermal method is developed to prepare hierarchical hollow precursors. An inside-out Ostwald ripening mechanism is proposed to explain the formation of the hollow structure. After the calcination in the air, hierarchically meso/macroporous NaCoPO4-Co3O4 hollow microspheres can easily be obtained. When being evaluated as electrode materials for a supercapacitor, the hierarchically porous NaCoPO4-Co3O4 hollow microspheres electrode shows a specific capacitance of 268 F g(-1) at 0.8 A g(-1) and offers a good cycle life. More importantly, the obtained materials are successfully applied to fabricate flexible solid-state asymmetric supercapacitors. The device exhibits a specific capacitance of 28.6 mF cm(-2) at 0.1 mA cm(-2), a good cycling stability with only 5.5% loss of capacitance after 5000 cycles, and good mechanical flexibility under different bending angles, which confirms that the hierarchically porous NaCoPO4-Co3O4 hollow microspheres are promising active materials for the flexible supercapacitor.