Benzo[1,2,3,4,5]tetrathiaselenepin is an unstable cyclic polychalcogenide. Isopropyl and/or methoxy groups at the neighboring of polychalcogen ring sterically stabilized the unstable ring. Replacing of aromatic unit from benzene to naphthalene also gave thermodynamic stability to the ring. Synthesis, characterization, and stability of some novel polychalcogenides are reported.