The sulfonic containing polymer bead was synthesized using sodium p-styrenesulfonate (SSS) and N,N′-methylenebisacrylamide (MBA) through inverse suspension polymerization and evaluated as catalyst for esterification of of n-octanol and acrylic acid. The influence of some principal factors, such as combination dispersant, crosslink agent content, posttreatment methods, and porogen types, was investigated in detail. The results showed that the morphology and characteristics of polymer beads were controllable. The polymer beads with 20wt% crosslink agent showed the best catalysis ability achieving almost 96% esterification conversion at the first time and 80% after 5 cycles.