As continuous consumption of the world's lithium reserves is causing concern, alternative energy storage solutions based on earth-abundant elements, such as sodium-ion batteries and zinc-air batteries, have been attracting increasing attention. Herein, nanoframes of CoO(x)are encapsulated into carbonized microporous fibers by electrospinning zeolitic imidazolate frameworks to impart both a sodium-hosting capability and catalytic activities for reversible oxygen conversion. The ultrahigh rate performance of sodium-ion batteries up to 20 A g(-1)and ultrastable cycling over 6000 cycles are attributed to a dual-buffering effect from the framework structure of CoO(x)and the confinement of carbon fibers that effectively accommodates cyclic volume fluctuation. Bothin situRaman andex situmicroscopic analyses unveil the reversible conversion of CoO(x)during the sodiation/desodiation process. The excellent ORR activity, superior to that of commercial Pt/C, is mainly ascribed to the abundant Co-N-C species and the full exposure of active sites on the microporous framework structure. Flexible and rechargeable sodium-ion full batteries and zinc-air batteries are further demonstrated with great energy efficiency and cycling stability, as well as mechanical deformability.