Abstract: Etoposidum:4′-demethyl-epipodophyllotoxin-β-D-ethylidene-pyrano-glucoside orVP-16-213 in trade name is a semisynthetic antineoplastic drug. We found that it has two differentkinds of crystal form named crystal A and B, they were crystallized from methanol and ethanol respec-tively. Their structures were identified by NMR and MS. They have similar infrared spectrum butwith repeatable small differences. The powder X-ray diffraction pattern of the two kinds of crystalsare quite different. The DSC curve of crystal A is rather smooth but that of crystal B shows abnormalpositive and negative peaks. On the other hand, they have the same kind of smooth TGA curves. Thisfact shows that the positive and negative peaks are not the result of chemical reaction. After heatingcrystal B in DSC oven at 190°C and 250°C ,respectively,their IR spectra showed that the pattern ofthe first one did not change, but the second one changed to the spectrum of crystal A. This reveals thatthe positive peak is due to the melting of crystal B and the negative peak is the result of the formationof crystal A. The pharmaceutic preparation of VP-16-213 is its glycerine solution, so the crystal formdoes not influence the efficacy of the drug.