The crystal and molecular structure of 1,8-thianaphthalene has been determined and compared with othersingle-atom peribridged naphthalenes (SAPN). The measured CSC angle is 73.06°, which is the smallest bridging angle yet recorded for a SAPN derivative. The ab initio calculations using G3(MP2)//B3LYP method were performed for peribridged naphthalenes in order to determine how the strain of the four-membered ringis influenced by the type of bridge linking 1,8 positions. The electronic structure of 1,8-thia-and1,8-sulfonenaphthalenes has been studied by UV photoelectron spectroscopy. We have tried to identify and distinguish the strain effect on the electronic structure of the naphthalene moiety.