Disclosed is 4-[(3-ethynylphenyl)amino]-6,7-benzo-12-crownquinazoline hydrochloride, known as icotinib hydrochloride, and new crystalline forms thereof. Also disclosed are methods for preparing icotinib hydrochloride, the XRPD diffraction pattern of the new crystalline forms, pharmaceutical compositions containing the compound, use of the compound for the treatment of cancer and the intermediates of the compound.