An ultraporous metal-organic framework (MOF)-based carbon nanofiber mat (CNFM4) with two types of hollow structure was prepared by electrospinning the mixed solution with polyacrylonitrile, polymethyl methacrylate and ZIF-8, followed by carbonization. The self-supporting CNFM4 has a higher Brunauer-Emmett-Teller (BET) specific surface area (SBET) (935.5 m2/g) and total pore volume (Vtotal) (0.69 cm3 g−1) than the PAN, PAN/PMMA, PAN/ZIF-8-derived carbon nanofiber mats (CNFMs). Static adsorption experiment showed CNFM4 had a high benzene adsorption capacity of about 12 mmol g−1 at saturated vapor pressure at 298 K, due to its high Vtotal. And even at low pressure of 0.1 kPa, its adsorption capacity still reached 2.75 mmol g−1, owing to its high SBET and rich micropore. The dynamic adsorption study showed CNFM4 has a breakthrough and saturation adsorption amount of 0.4902 and 0.5714 mmol g−1 at dry gas, respectively, and even at 60 RH%, they still can keep 0.2620 and 0.3642 mmol g−1, respectively, suggesting its application potential under the actual environment. The dynamic adsorption study also proves the important role of hollow structure at improving adsorption rate. This work provides a new idea for preparing the ultraporous MOF-based hollow CNFMs, and broadens the application of MOF-based CNFMs for VOCs removal.