This article describes the structure-induced quantum confinement effect in nanostructured crystals, a unique class of hybrid semiconductors that incorporate organic and inorganic components into a single-crystal lattice via covalent (coordinative) bonds to form extended one-, two- and three-dimensional network structures. These structures are comprised of subnanometer-sized II-VI semiconductor segments (inorganic component) and amine molecules (organic component) arranged into perfectly ordered arrays. The article first provides an overview of II-VI and III-V semiconductors, II-VI colloidal quantum dots, inorganic-organic hybrid materials before discussing the design and synthesis of I-VI-based inorganic-organic hybrid nanostructures. It also considers the crystal structures, quantum confinement effect, bandgaps, and optical properties, thermal properties, thermal expansion behavior of nanostructured crystals.