A mononuclear terbium coordination compound(Tb1-A) was prepared from t-tert-butyl-sulfonylcalixarene(H4TC4A-SO2) and Tb(CH3COO)3. Calixarene can effectively sensitize terbium ions, enabling luminescence of Tb1-A in both solid state and methanol solution. It was found that 1,10-phenanthroline(phen) could influence the luminescence of Tb1-A by two interaction modes in fluorescence titration. Two different contacting modes between phen and Tb1-A were also determined by the single crystal structural characterization of two mononuclear compounds(Tb1-B and Tb1-C), one of which was the coordination between phen and Tb ions, the other was the host-guest interaction between phen and calixarene. Combined with the results of theoretical calculation, it was also found that the host-guest interaction between guest molecules and calixarene was the main factor that caused the fluorescence quenching.