Activated carbon fibers are a kind of microporous carbon. Using dangling bond spins attached to the peripheries of the micropores, we investigated the microporous structures in relation to the heat-treatment and gas adsorption effects. Functional groups weakly bonded to the graphitic backbone are removed by the heat-treatment at moderate temperatures 200-400°C, resulting in the generation of a variety of dangling bond spins. The heattreatment above 500°C brings about homogenization of the dangling bond spins. For gas adsorption, the introduction of helium gas strongly enhances the spin-lattice relaxation rate for the dangling bond spins. In addition to a remarkably large condensation of helium gas in the microporous region, the enhancement proves the presence of ultra-micropores which can accommodate only the smallest diameter helium atoms.