Chalcogenation reactions of 1,2-bis(fenucenyl)diphosphene, Fc*P=PFc* (Fc*: 2,5-bis(3,5-di-t-butylphenyl)ferrocenyl), with elemental sulfur (S-8) and tellurium afforded the corresponding thia- and telluradiphosphirane derivatives as stable crystalline compounds, respectively. The sterically demanding ferrocenyl group would afford sufficient crystallinity and stability to the heterocyclic compounds; the structures of these three-membered ring heterocycles were revealed by X-ray crystallographic analysis.