Facile synthesis of porous and hollow spinel materials is very urgent due to their extensive applications in the field of energy storage. In present work, flowerlike porous LiFeO microspheres etched for 15, 30, and 45 min (named as p-LFO-15, p-LFO-30, and p-LFO-45, respectively) are successfully synthesized through a facile chemical etching method based on bulk LiFeO (LFO) particles as precursors, and they are applied as electrode materials for high-performance electrochemical capacitors. In particular, the specific surface area of p-LFO-45 reaches 46.13 m g, which is 112 times greater than that of the unetched counterpart. Therefore, the p-LFO-45 electrode can achieve a higher capacitance of 278 F g at a scan rate of 5 mV s than the unetched counterpart. Furthermore, the p-LFO-45 electrode presents a good cycling stability with 78.3% of capacitive retention after 2000 cycles, which is much higher than that of the unetched LFO particles (66%). Therefore, the flowerlike porous LFO microspheres are very promising candidate materials for supercapacitor applications.