2,2':6',2"-Dioxa- and dithia-triphenylamines 4a and 4b were prepared. Both compounds had a C-2-like structure. The sulfur compound 4b had a more twisted structure than 4a; the dihedral angle between two edge phenyl rings was 43degrees for 4a, and 62degrees for 4b. The oxygen compound 4a had a reversible oxidation wave at +0.81 V vs SCE, whereas 4b had an irreversible peak at +1.14 V.