Highly active,air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents.Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes(POPd) and phase transfer catalyst(tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture,water/propanol mixture and neat water respectively,the corresponding yields of cross-coupling heteroaryl-aryls were satisfied.The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2,and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3.The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step.Compared with other solid phase transfer catalysts,TBAB was tested as the ideal one.The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents.Notably,in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products.However in terms of the liquid phase transfer catalyst of PEGs,mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase,which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths. Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water / alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water / ethanol mixture, water / propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl- aryls were satisfied. substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipdazolium POP1 and POPd2, and the other two kinds of Pd-catalysts Pd (PPh3) 4 and Pd2 (dba) 3.The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer c atalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding Often in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yield with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular length lengths.