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Most of the hollow carbon submicro-fibers (HCSFs) reported today are made from polyacrylonitrile (PAN) homopolymer. The obtained HCSFs are fragile due to the poor stabilization and spinnability of PAN. In this study, a bifunctional comonomer, β-methylhydrogen itaconate (MHI), was synthesized to prepare poly(acrylonitrile-co-β-methylhydrogen itaconate) [P(AN-co-MHI)] copolymer, which was used as a precursor to produce HCSF by coaxial electrospinning. The stabilization of P(AN-co-MHI) was studied by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR); the structure of HCSFs was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and field emission scanning electron microscopy (FE-SEM). The stabilization of P(AN-co-MHI) has been improved significantly by MHI with lower cyclization temperature, broadened peak and lower activation energy, which is beneficial to producing high-performance HCSFs. HCSFs with fine and uniform structures were obtained after stabilization and carbonization; the diameter of the HCSFs shrinks due to the elimination of N and the extra H. The diameter and wall thickness of HCSFs can be controlled simply by the feeding ratio of P(AN-co-MHI) solution/styrene-co-acrylonitrile solution. The resultant HCSFs can be bent more than 280° without breaking, which has potential applications in lithium-ion rechargeable batteries, supercapacitors, fuel cells, and catalyst. [ABSTRACT FROM AUTHOR]