A series of 2-aryl-1,3-benzothiaphospholes have been synthesized from 1-mercapto-2-phosphinobenzene and a variety of acid chlorides. The structure of 2-phenyl-1,3-benzothiaphosphole was established using X-ray diffraction. The electrochemical and photophysical properties of each benzothiaphosphole are reported and some of these molecules exhibit reversible 1-electron reductions.