Macroporous styrene-divinylbenzene (St-DVB) copolymer beads are prepared with a novel pore-forming agent, 1-chlorodecane. Copolymer beads with high specific surface area are obtained although 1-chlorodecane is a typical incompatible solvent of polystyrene. The unexpected behavior of 1-chlorodecane during preparation of copolymer beads is discussed. It is found that the excellent compatibility between the chloro substituents in 1-chlorodecane and phenyl rings in copolymer could be responsible for the unexpected behavior. In addition, the effect of crosslinking density on the pore morphology of the copolymer beads is systematically investigated. The results indicate that the specific surface area, the total pore volume and the average pore diameter of the copolymer beads strongly depend on the crosslinking agent concentration. Overall, the present study provides a novel route to prepare macroporous polymer beads with controllable pore morphology. (C) 2010 Elsevier B.V. All rights reserved.