The aim of this study is to develop a new sampling technique based on microdialysis sampling technique prior to high performance liquid chromatographic (HPLC) analysis for monitoring toxic chemicals in workplace.A polyethersulfone (PES) hollow fiber microdialysis modules filled with ethylene glycol as absorption solvent in the shell-side was applied as the sampling tube to collect toxic pollutants from gas stream in the tube-side of hollow fiber dialysis modules through the equilibrium between gas stream and absorption solvent.Benzene and phenol were used as model species.The generation of standard gas stream was also designed and evaluated.