This article presents modeling and experimental study on the sulfonation of alkylbenzene to synthesize alkyl benzene sulfonate in a rotating packed bed (RPB) reactor. The effects of some important operating and reactor parameters, such as rotating speed of RPB reactor, liquid flow rate, SO3 molar concentration in sulfonating agent, reaction temperature, and packing thickness of RPB on the alkylbenzene sulfonated ratio were investigated. In addition, a coalescence-redispersion mathematical model was established to predict alkylbenzene sulfonated ratio in RPB, and the validity of the model was confirmed by the fact that most of the predicted alkylbenzene sulfonated ratio agreed well with the experimental data with a deviation within 12%. The experimental and numerical results showed that an improvement of the alkylbenzene sulfonation performance in RPB reactor could be achieved by optimizing the RPB rotating speed and total reactant liquid flow rate, decreasing the SO3 concentration in sulfonating agent and properly increasing the react temperature and RPB packing thickness.