By self-assembly in aqueous solution, calix- (CAS) and thiacalix[4]arene-p-tetrasulfonate (TCAS) formed luminescent complexes Tb III ·(CAS) 2 and Tb III ·TCAS, respectively, which were utilized as a host for cationic guests. Addition of 1-ethylpyridinium guest quenched luminescence of Tb III ·(CAS) 2 in accordance with the Stern-Volmer (SV) relation with a low detection limit (D.L.) of 5.94×10 −8 M (S/N=3, M≡moldm −3 ). On the other hand, 1-ethylquinolinium quenched luminescence of Tb III ·TCAS most efficiently, affording a very low D.L. (6.71×10 −10 M). The agreement of the SV coefficients obtained with luminescent intensity (K SV,all =6.74×10 6 M −1 ) and lifetime (K SV,Tb =6.50×10 6 M −1 ) implied that dynamic quenching of 5 D 4 excited state of Tb III was predominant in the quenching processes. The quenching rate was estimated to be k q,Tb =9.94×10 9 M −1 s −1 , which was as fast as diffusion-limited rate. Quenching of Tb III ·(CAS) 2 was also applied to detection of NAD + , with a D.L. of 2.78×10 −7 M.