This review summarizes the structural and synthetic aspects of heterocyclic molecules incorporating an atom of a hypervalent main-group element. The term "hypervalent" has been suggested for derivatives of main-group elements with more than eight valence electrons, and the concept of hypervalency is commonly used despite some criticism from theoretical chemists. The significantly higher thermal stability of hypervalent heterocycles compared to their acyclic analogs adds special features to their chemistry, particularly for bromine and iodine. Heterocyclic compounds of elements with double bonds are not categorized as hypervalent molecules owing to the zwitterionic nature of these bonds, resulting in the conventional 8-electron species. This review is focused on hypervalent heterocyclic derivatives of nonmetal main-group elements, such as boron, silicon, nitrogen, carbon, phosphorus, sulfur, selenium, bromine, chlorine, iodine(III) and iodine(V).