The fluorescence properties of europium and terbium in the calix [4 ] arene sulfonate and Phen-Dbm-complex system were investigated by fluorescence spectra. The maximum characteristic emission wavelength of Eu-Tb-DBMPhen complex system is 611 nm by using 370 nm excitation. The results show the synergistic luminescence effect of Eu3+ and Tb3+. The fluorescence intensity can be reduced when calix[ 4 ] arene is added.