Methyl methacrylate-divinylbenzene copolymer beads were synthesized by radical suspension polymerization. The effects of the divinylbenzene concentration and the composition of the toluene/heptane diluent were studied with regard to the polymer bead formation, surface morphology, solvent swelling ratio, and absorption kinetics. The crosslinking density and diluent composition were responsible for solvent swelling. The interaction between the polymer and the diluents is attributed to phase separation, which controls the formation of a network-type or pore-type polymer, or a combination. For the optimum bead swelling in toluene, a combined morphology of more flexible polymer networks and a small amount of pores is essential for the desired absorption-desorption behavior. Dynamic swelling behavior of the polymer beads was elucidated. The mechanism of toluene transport into the beads became more a relaxation control.