There has been great interest in compounds with double bonds between heavier group 15 elements due to their unusual properties. We achieved the synthesis and characterization of the first stable distibene (ArSb=SbAr) and dibismuthene (ArBi=BiAr) using bulky Tbt and Bbt groups. The cyclic voltammograms of dipnictenes (1b–3b) revealed reversible one-electron reductions, with distibene showing the lowest reduction potential. The anion radical species of 1b and 2b were synthesized and isolated as stable crystalline compounds via Li reduction, and the distibene radical (2b) was structurally confirmed by X-ray analysis. These π-bond systems of heavier group 15 elements display remarkable redox behavior. Furthermore, 1,2-bis(ferrocenyl)dipnictenes (4–6) were synthesized as novel bimetallic d–π electron systems. Recent advances in low-coordinated heavier group 15 species will be discussed.