Abstract: The studies of olefin hydroformylation in aqueous/organic bi-phase catalyzed by water soluble RhCl(CO)(TPPTS)₂-cationic surfactant complex system was introduced.The acceleration of the reaction by cationic surfactant was connected with the mechanism of meta-stable micellar-ionic pair synergistic action.The enrichment of rhodium catalyst on the micellar interface and solubilization of olefin in hydrophobic core of micelle created a very favorable microcircumstance for olefin coordination with rhodium complex.Therefore the high region-selective and high active rhodium catalyst systems could be designed and prepared by molecular assembly on biphasic interface.The modification of catalytic performance of rhodium complex was realized by the application of CTAB-SDS mixed surfactants and TPPTS-TPPDS mixed ligands.TOF(turnover frequency,h^-1)and normal/isomer aldehyde ratio (n/i)in 1-dodecene hydroformylation catalyzed by the modified rhodium catalyst reached 200—350 h^-1 and 18—40,respectively.The matching effect between chain length of olefin and surfactant was discovered.If both the chains length were similar the catalyst had high region-selectivity.When cationic surfactant with double long chain combined with water soluble rhodium phosphine complex, the catalyst system exhibited high activity and TOF of 1-dodecene hydroformylation could reach over 1000 h-1 even without stirring.