Butyl methacrylate/hydroxyethyl methacrylate (HEMA) copolymeric fiber was prepared by gelation-spinning in twin screw extruding machine, the swelling behavior, absorptive kinetics, and crystallization behavior were investigated, finally the morphology was observed by SEM. The results show that absorptive rate can be quickened and absorbency can be increased with an increase in mass fraction of HEMA. Under the same condition, the fiber has greater capability to absorb chloroform and trichloroethylene, but it has relatively weaker capability to absorb toluene. Additionally, the fiber can selectively absorb toluene from mixed system with high efficiency during a short time. When mass fraction of HEMA is 10 wt% or 15 wt%, Eq. 7 can well describe absorptive kinetics. The polymer melt cannot assume a crystalline structure under the cooling shaping condition during the spinning process, but the melt can form crystals in the cooling process after the fiber has absorbed chloroform for 24 h. The surface becomes coarser and coarser, and the cross section becomes irregular with an increase in mass fraction of HEMA, what is more, number of cavities on the surface and cross section increases as mass fraction of HEMA increases.