Efficient electrode material is crucial for energy conversion from renewable sources such as solar electricity. We present a method for preparation of carbon nanotubes(CNTs) with zeolitic imidazolate frameworks(ZIFs, e.g., ZIF-8) via an in situ pyrolysis process. The resultant materials are completely new carbon composites with desirable hierarchical porosity and nitrogen-doped features. Electron microscopy images show that CNTs with small external diameters enable more uniform dispersion of ZIF-8-derived carbons, subsequently yielding a unique hierarchically porous structure. Such carbon shows superior activity in oxygen reduction reaction(ORR) and high performance of supercapacitance, making it a valuable metal-free electrode material and a competent alternative to the state-of-the-art Pt/C catalyst. The electrocatalytic performance of CNTs can be dramatically improved by the incorporation of ZIF-8-derived carbons, which is attributed to the combination of good conductivity, abundant accessible dopant species, as well as proper porosity. Our method offers a new avenue for constructing electrocatalysts by effective integration of ZIF-8-derived carbon and the CNTs skeleton. Efficient electrode material is crucial for energy conversion from renewable sources such as solar electricity. We present a method for preparation of carbon nanotubes (CNTs) with zeolitic imidazolate frameworks (ZIFs, eg, ZIF-8) via an in situ pyrolysis process. Materials are completely new carbon composites with desirable hierarchical porosity and nitrogen-doped features. Electron microscopy images show that CNTs with small external diameters enable more uniform dispersion of ZIF-8-derived carbons, subsequently yielding a unique hierarchically porous structure. Such carbon shows superior activity in oxygen reduction reaction (ORR) and high performance of supercapacitance, making it a valuable metal-free electrode material and a competent alternative to the state-of-the-art Pt / C catalyst. The electrocatalytic performance of CNTs can be dramatically improved by the incorporation of ZIF-8-derived carbons, which is attributed to the combination of good conductivity, abundant accessible dopant species, as well as proper porosity. Our method offers a new avenue for constructing electrocatalysts by effective integration of ZIF-8-derived carbon and the CNTs skeleton.