In this paper, the conventional fluorescence spectra and laser induced fluorescence spectra of a novel macrocyclic dioxotetramine, 1,4,7,10-tetraazacyclotridecane-11,13-dionato and its Cu(II), Co(II), Ni(II) complexes at different pH are studied. The results show that the complexes fluorescence quantum yields have the relation of phi CuL5 < phi CoL5 < phi NiL5. At the same time, the reasonable explanation is given. The correspondence between their catalytic activities and fluorescence spectra character as minic superoxide dismutase metalloenzynes are also analyzed. It has been found that the fluorescence quantum yield of CuL5 decreases when the pH gets higher. But it is on the contrary for CoL5 and NiL5. It has been inferred that catalytic activities may be CuL5 > CoL5 > NiL5 according to their fluorescence quantum yield.