2,3-Diphenyl-1,4-benzodithiin (1) was prepared from the reaction of phenyl-lithium and bromobenzene with carbon disulphide. 2-(Biphenyl-2-yl)-3-phenyl-1,4-benzodithiin (2), 3-(biphenyl-2-yl)-2-phenylbenzo[b]thiophen (3), and 2,3-dihydro-2,3-diphenyl-1,4-benzodithiin were isolated as by-products. Pyrolysis of (1) afforded tetraphenylthiophen. A reaction mechanism involving a benzyne intermediate is suggested.