Abstract: Identification and determination of polyamines (e.g., propane-1,3-diamine, putrescine, spermidine, spermine, cadaverine and homospermidine) present in Chinese caterpillar fungus (Cordyceps sinensis Sacc.) was carried out by HPLC, GC and GC - MS. Powdered sample (10 g) was treated with 1 M HClO4 and separated on columns of Dowex-50 W-X8 (4 cm x 2 cm) and CM-Cellulose (0.8 cm x 0.5 cm). The resulting solution was analyzed by HPLC on a 62110 FK column (8 cm x 4.6 mm) with post-column derivatization (details given); elution was effected with a mobile phase of KCl - K citrate solution (37.275:108.137) and fluorescence detection was at 450 nm (excitation at 365 nm). For determination, the resulting solution was acylated with heptafluorobutyric anhydride, before analysis by GC and GC - MS on a column of 3% SE-30 and 70-eV MS detection. Results were tabulated.