The study aimed at preparing porous carbon materials, with superhydrophilic characteristics and developed micro/mesoporous structure (CSB-800), from corn stover by a solvent-free method including pre-carbonization, ball milling, and activation. The effect of pre-carbonization, ball milling on the detailed structural composition and properties especially the hydrophilicity and porous structures were studied, and the potential application of CSB-800 as electrode in supercapacitors was also investigated. The results revealed that pre-carbonization increased the accessibility of raw materials as well as the efficiency of the ball milling with KOH, leading to small carbon particles with good dispersion behavior. Ball milling promoted the porosity, surface energy, hydrophilicity, crystallinity, and graphitization of the carbon materials. CSB-800 exhibited a high specific surface area of 2440.6 m<
sup>
2<
/sup>
/g with developed micro and porous structures. The heteroatom nitrogen formed nitrogen-containing groups of N<
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Q and N<
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X, which provided faradaic pseudocapacitance when CSB-800 was used as an electrode material, and this material presented a specific capacitance of 398 F/g at 0.5 A/g in 1 M H<
sub>
2<
/sub>
SO<
sub>
4<
/sub>
electrolyte in a three-electrode system, while the value was 243 F/g in a two-electrode system, and the energy density reached 5.01 Wh/kg at a power density of 100 W/kg.