Bismuth oxide (Bi 2 O 3 ) with high specific capacity has emerged as a promising negative electrode material for supercapacitors (SCs). Herein, we propose a facile metal-organic framework (MOF) derived strategy to prepare Bi 2 O 3 microrods with a carbon coat (Bi 2 O 3 @C). They exhibit ultrahigh specific capacity (1378 C g -1 at 0.5 A g -1 ) and excellent cycling stability (93% retention at 4000 cycles) when acting as negative electrode material for advanced asymmetric SCs. The assembled Bi 2 O 3 @C//CoNi-LDH asymmetric supercapacitor device exhibits a high energy density of 49 W h kg -1 at a power density of 807 W kg -1 . The current Bi-MOF-derived strategy would provide valuable insights to prepare Bi-based inorganic nanomaterials for high-performance energy storage technologies and beyond.