In this paper, bamboo-like, O-doped carbon tubes with hierarchical pore structure have been fabricated by the direct pyrolysis of dual cross-linked polydivinylbenzene (PDVB) tubes. The bamboo-like, cross-linked PDVB tubes are firstly synthesized by cationic polymerization of divinylbenzene in cyclohexane using BF3/Et2O complex as the initiator. After a secondary cross-linking being imposed by Friedel-Crafts reaction in CCl4 using anhydrous AlCl3 as the catalyst, the obtained dual cross-linked, carboxylic acid functionalized PDVB tubes are directly subjected to pyrolysis, yielding bamboo-like, O-doped porous carbons. The resultant O-doped porous carbon tubes (BCTF-900, pyrolyzed at 900 A degrees C) exhibit a trimodal pore structure (micro-, meso-, and macropores) with a relatively high specific surface area of 595 m(2) g(-1) and a low total pore volume of 0.37 cm(3) g(-1). Such bamboo-like carbon tubes display good volumetric capacitive performance (254 F cm(-3) at 0.5 A g(-1)), moderate volumetric energy density (12.9 Wh L-1 at 428 W L-1), and excellent cycling stability (the capacitance retention has remained at 96.9% after 10000 cycles at 2 A g(-1)). Due to their unique bamboo-like architecture and trimodal pore structure, the PDVB-derived carbon tubes should have widely application prospect.