Cu2+, Fe2+ and Fe3+ could chelate with cyclodextrin-modified hypocrellin (HBCD) efficiently and the UV-visible spectra of the resultant metal complexes red shifted by more than 40 nm. ESR study revealed that the hydroxyl radical was the main product during irradiation of these metal complexes because Cu2+, Fe2+ and Fe3+ initiated the Fenton reaction. Also, these metal complexes photodamaged the calf thymus DNA in the liposome system 20 folds faster than that in the buffer solution due to the initiation of lipid peroxidation.