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2-(Trimethylsilyloxy)ethyl methacrylate (SMA)-derived mesoporous carbon nanofiber composite containing MnO 2 (Si-Mn-CNF) is fabricated by electrospinning method and found to be a very promising candidate for supercapacitor electrodes. Si-Mn-CNF possesses a large surface area of 707 m 2 g − 1 , high pore volume of 2.35 cm 3 g − 1 , and high mesopore fraction of 65%. Herein, SMA is used as an activating agent to develop the mesoporous structure by the thermal decomposition of SMA without activation process. As a result, Si-Mn-CNF exhibits a high specific capacitance of 200 Fg − 1 at a discharge current density of 1 mAcm − 2 and energy density of 23.72 Whkg − 1 at a power density of 400 Wkg − 1 in 6 M KOH aqueous electrolyte, due to the pseudocapacitive character associated with the surface redox-type reactions of the MnO 2 nanoparticles (NPs). Furthermore, the Si-Mn-CNF electrode retains a specific capacitance of over 85% of the initial value at a discharge current density of 20 mAcm − 2 compared with only 40% for Mn-CNF without using SMA, due to the rapid diffusion of electrolyte ions and the decrease of resistive characteristics through the developed mesoporous structures. Therefore, Si-Mn-CNF with high mesoporosity induced by SMA exhibits excellent electrochemical performance in terms of high specific capacitance and energy density, and excellent capacitance retention. [ABSTRACT FROM AUTHOR]