Hollow Fiber flow field-flow fractionation (HF-FlFFF) has been tested in polyacrylonitrile (PAN) membrane channel in order to compare it with polysulfone (PSf) membrane channel. It has been experimentally shown that the separation time of 0.05-0.304 µm polystyrene latex (PSL) standards in PAN membrane channel is shorter than that in PSf channel by approximately 65%. The optimized separation condition in PAN membrane is = 1.4/0.12 mL/min, which is equal to the condition in PSf membrane channel. In addition both the resolution (R s ) and plate height (H) in PAN membrane channel are better than that in PSf membrane channel. The membrane radius was obtained by back calculation with retention time. It shows that the PSf membrane is expanded by swelling and pressure, but the PAN membrane doesn't expand by swelling and pressure.