Herein, we demonstrate a facile method for the preparation of microporous organic nanotubes (MONTs) based on a combination of hyper-cross-linking mediated self-assembling strategy and Scholl reaction by using polylactide-b-polystyrene diblock copolymers (PLA-b-PS) as precursors, in which the PS block forms the microporous organic frameworks of nanotubes through the C–C coupling reaction, while the PLA segment is completely degraded to produce the hollow mesoporous tubular structure. Owing to their high special surface area, robust organic framework and open-ended tubular structure, the obtained MONTs exhibit the outstanding adsorption capacity and efficiency for p-cresol and different organic vapors. Moreover, microporous carbon nanotubes (MCNTs) can be prepared by further carbonization. The resultant MCNTs as electrode materials of a supercapacitor display excellent electrochemical performance with specific capacitances of up to 192 F g–1 at 0.5 A g–1, with capacitance retention of 97% even after 5000 cy...