New di- (2) and tetracarboxylate ligands (4) were prepared on a sulfonylcalix[4]arene platform by O-alkylation of thiacalix[4]arene with ethyl bromoacetate, followed by hydrolysis of the ester function and oxidation of the sulfide bridges. The sulfonyl-based ligands 2 and 4 formed luminescent 1:1 complexes with terbium(III) ion having higher luminescent quantum yield (Φ=0.29 1 and 0.28 7 , respectively) than 1:1 complexes of the corresponding thiacalix[4]arene-based di- (1) and tetracarboxylate ligands (3) (Φ=0.03 8 and 0.00 3 , respectively), implying higher efficiency of sulfonyl ligands (2 and 4) than those of thia ligands (1 and 3) in the energy transfer process.