The DNA-binding behaviors of the fluorescein–porphyrinatozinc(II) complex Zn(Fl-PPTPP) (Fl-PPTPP = 5-(4-fluoresceinpropyloxy)phenyl-10,15,20-triphenylporphyrin) and fluorescein–porphyrinatocopper(II) complex Cu(Fl-PPTPP) with calf thymus DNA (CT-DNA) were investigated by UV–Vis absorption titrations, fluorescence spectra, viscosity measurements, thermal denaturation and circular dichroism. The results suggest that both complexes interact with CT-DNA by intercalation. In addition, their photocleavage reactions with pBR322 supercoiled plasmid DNA were investigated. Both complexes exhibit significant DNA cleavage activity, and singlet oxygen may play an important role in these reactions.