The hydrodynamic characteristics and mass transfers of halide quaternary salts between two immiscible phases in a stirred membrane permeation cell were investigated. The concentration of quaternary salt, temperature, solvent and the four kinds of halide quaternary salts were evaluated to achieve the extractive optimum condition. The diffusivity, overall mass-transfer coefficients and individual mass-transfer coefficients were determined and correlated in terms of the conventional Sh-Re-Sc relationship. The transfer time of quaternary salts across the membrane and the thickness of the hydrodynamic diffusion boundary layer were determined as well, so as to characterize the extractive phenomenon of quaternary salts between the two phases that is useful in phase-transfer catalysis.