Incorporation of main group elements into the it-conjugated frameworks is a sophisticated strategy to alter the fundamental nature of the parent conjugated pi systems, giving rise to attractive electronic and photophysical properties that are otherwise inaccessible with classic carbon- or metal-based materials. Out of all irconjugated heterocycles, those that are structurally constrained by tethered aryl substituents surrounding the main group center deserve a great deal of attention because not only do they commonly possess the maximum efficiency of it -conjugation and intermolecular interaction, but they also enjoy remarkable thermal and morphological stabilities that are especially crucial for solid-state performances. In certain cases, elucidation of the behavior of such compounds may additionally provide sufficient perspective toward graphene materials doped with main group elements, which are widely considered as potential next -generation optoelectronic materials. In this review, we will specifically focus on historical developments of structurally constrained polycyclic it -electron systems particularly of those with boron, nitrogen, silicon, or phosphorus atoms annulated directly into the center of 2r -conjugated systems.