The synthesis, structure, and optical and electrochemical properties of thiophene-containing hybrid calixphyrins are reported. The 5,10-porphodimethene type 14 pi- and 16 pi-S,N(2),X-hybrid calixphyrins (X = NH, O, S) were prepared by acid-promoted dehydrative condensation between a thiatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both crystallographic and spectroscopic analyses of the newly prepared hybrid calixphyrins have revealed that the combination of heteroles explicitly influences the electronic structures of the pi-conjugated framework. The 14 pi-S,N(2),X-hybrid calixphyrins have proven to be fluorescent in solution.