Exploring the method for rational design hierarchical structures such as hollow, sphere and core-shell structure is a crucial challenge for enhancing electrochemical performance of supercapacitor electrodes. In this study, we demonstrate a facile method for controllable preparation of hydrangea shaped CoAl-LDHs@CoF2 composite and used as positive electrode for supercapacitor. A series of contrast tests are performed to select optimal experiment condition. CoAl-LDHs obtained at metal ratio of 2:1, reacting 8 h with addition of NH4F, displays optimal performance associated with the hierarchical structure, where NH4F plays a vital role in regulating this uniform generation process. The fabricated working electrode shows high specific capacitance of 827.8 Fg −1 , with excellent capacitance retention of 62.8% after current density increases ten times. At last, an asymmetric supercapacitor using C2A1-8h sample as positive electrode and activated carbon as negative electrode, is assembled and delivers an outstanding energy density of 53.7 Wh kg −1 at power density of 239.9 kW kg −1 , and energy density reaches 27.8 Wh kg −1 at maximum power density of 12000 W kg −1 , indicating C2A1-8h is a potential candidate for energy storage and conversion systems.