The smooth and uniform polymer of intrinsic microporosity (PIM-1) fibers, which have high adsorption capacities toward organic contaminants from nonaqueous systems, were successfully obtained by electrospinning. According to the N-2 adsorption-desorption analysis, the surface area of the PIM-1 fibers was higher than that of the PIM-1 powder. The higher surface area of the fibers did not come from the interfiber pores but from intrafiber pores formed by the fast evaporation of the solvent in the electrospinning process. The PIM-1 fibers had more mesopores than the PIM-1 films. As a result, the adsorption rates of the dyes on the fibers were much higher than those on the dense films. We found that the adsorption data fitted perfectly with the pseudo-second-order model and intraparticle diffusion model. The adsorption mechanism between the dyes and PIM-1 was p-p interaction. Therefore, the dye could be desorbed from PIM-1 with toluene; this was a better p-electron-rich donor than the dye. In summary, we believe that the use of PIM-1 fibers for organic solvent recovery is a green, sustainable, and efficient method, and they have a great potential for industrial applications. (C) 2016 Wiley Periodicals, Inc.