Abstract: GTX1/4 and GTX2/3 are the most harmful algal toxins in the coastal waters of China. The paralytic shellfish toxins from mussel samples were extracted with 0.18 mol/L formic acid aqueous solution, cleaned up with ethyl acetate and trichloromethane. Then, the crude PSTs solutions were separated by macroporous adsorption resin SP700 and purified by preparative high performance liquid chromatographic (PHPLC) coupled with Hillic column. It developed an effective method for the preparation of paralytic shellfish toxins reference materials.