In this review, we discuss the rich chemistry of helicenes and helicenoids containing main-group elements. Enantioenriched helicenic derivatives containing main-group elements B, Si, N, and P, either incorporated within the helical backbone or grafted to it, will be thoroughly presented. We will describe their synthesis, resolution, and asymmetric synthesis, their structural features, electronic and chiroptical properties, and emission, together with other photochemical properties and applications.