1-Dodecene hydroformylation catalyzed by water-soluble rhodium complex, RhCl (CO) (TPPTS) [TPPTS: P (m-C6 H4 SO3 Na)3], in the presence of surfactants and alcoholic solvents was studied. The results indicated that the hydroformylation in biphasic catalytic system occurred in the interface of aqueousrorganic phases. The formation of micelle was not only favorable for the reaction acceleration, but also favorable for the increase of linear aldehyde ratio in products. The key factor of the enhancement of reaction rate was the richness of rhodium catalyst in the interlayer with the static electricity attraction between active rhodium anion species and cationic end of surfactant.