Quinoidal π-conjugation usually possess long-wavelength absorption and multistage redox properties which make it as promising organic electronic materials. In addition, incorporating heteroatoms into conjugated skeleton is an intriguing target because the introduction of heteroatoms would induce a variety of intermolecular interactions, such as van der Waals interactions and heteroatom-heteroatom interactions (S • • •S or Se• • • Se interactions), which is essential to achieve highly ordered supramolecular self-assembled structure and eventually excellent device performance. Herein, a facile route has been developed for the preparation of meso-position sulfur embedded quinoidal bisanthene 1. Thione 3 were prepared from corresponding thioxanthen-9-one via reaction with Lawesson’s reagent followed by the Barton-Kellogg reaction with 9-diazothioxanthene derived from corresponding hydrazine to afford the thioepoxides 5. The resulting compound 5 were then treated with copper powder to give the desired olefin precursor 6. Katz-modified Mallory photocyclization was carried out on 6 for the purpose to obtain the target molecule 1. The reaction was conducted by irradiation of the benzene solution of 6 with a 450 W medium-pressure mercury vapor lamp in the presence of I2 and propylene oxide. Unfortunately, only the partially cyclized product 7 were obtained in 77% yield. The reason leading to this result is that there is no more stilbene structure in compound 7. This partially cyclized product 7 showed extended π-conjugation compared with its olefin precursors 6 and exhibited 105 nm and 90 nm red shift of the corresponding absorption maxima and emission maxima. In addition, compound 7 can be oxidized into charged states which are stabilized by the delocalized π-system.