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This Review discusses the structure-property relationships in chiral molecules, macromolecules (polymers), and supramolecules (crystals, liquid crystals, or thin films) containing main-group elements. Chirality is a major property in our world, having a prominent influence on processes in biology, chemistry, and physics. Its impact in optics due to its interaction with electromagnetic waves gave rise to a multitude of effects, such as the Cotton effect and circularly polarized luminescence, making possible applications such as 3D displays and polarized sunglasses. Herein, a particular emphasis will be given to the influence of chirality on the conducting and optical properties of molecules or materials containing frontier heteroelements, particularly boron, silicon, phosphorus, and sulfur. These synergic materials are expected to become game-changers in the field of materials science by bringing new properties into the realm of reality, such as chirality-induced spin-selectivity, circularly polarized luminescence, and electrical magnetochiral anisotropy. This Review should be of interest for chemists and also physicists working in the fields of molecular and supramolecular chemistry, and molecular materials in the broadest sense.