This chapter summarizes recent advances made by two types of cyclic organobismuth compounds, sulfone- and sulfoximine-bridged dibenzobismines and tetrahydrodibenzazabismocines, in the field of organic synthesis. The cyclic frameworks of these organobismuth compounds possessing heteroatom-bridged bis(aryl) ligands are highly stable but keeping flexibility and allowed the development of highly useful stoichiometric and catalytic reactions. Although arylbismuth compounds have long been known as useful arylating reagents, sulfone-bridged bismine reagents significantly improved the selectivity, efficiency and practical usefulness of the arylation reactions by organobismuth compounds. Catalytic applications of bismines include the first homogeneous Bi(III)/Bi(V) redox catalysts for the synthesis of fluoroarenes and aryl triflates and nonaflates. Redox neutral catalysts for the synthesis of arylsulfonyl fluorides were also developed. A cationic azabismocine was found to act as a catalyst for the amide reduction with hydrosilanes. Difluorocyclopropanes and -cyclopropenes were efficiently synthesized using Bi-CF3 azabismocine as a catalyst. Oxidation of thiols to disulfides was also catalyzed by azabismocines.