Recently, tremendous efforts have been devoted to creating inexpensive porous carbon materials with a high specific surface area (SSA) as adsorbents or catalysts for the efficient removal of organic pollutants. Here, activated porous carbon fibers with hierarchical structures were designed and constructed by an electrospinning technique, in situ polymerization, and activation and carbonization processes. Benefiting from the precursor fiber design and subsequent activation techniques, the activated porous carbon fibers (APCFs) derived from a benzoxazine/polyacrylonitrile (BA-a/PAN) precursor exhibited an ultrahigh SSA of 2337.16 m 2 g -1 and a pore volume of 1.24 cm 3 g -1 , showing excellent adsorption capacity toward methylene blue (MeB, 2020 mg g -1 ). Interestingly, the APCFs after pre-adsorption of MeB also display robust activation of peroxymonosulfate (PMS) with singlet oxygen for the ultrafast removal of MeB. Meanwhile, the synergistic effect of adsorption and a catalytic oxidation reaction using APCFs can realize outstanding total organic carbon (TOC) removal in a comparatively short time. Moreover, a synergistic adsorption-oxidation mechanism for promoting the removal of MeB using APCFs was proposed. This study is useful for the design and development of novel metal-free carbon adsorbents, catalysts or catalyst carriers with an ultrahigh SSA for various applications.