Two-dimensional organic–inorganic halide perovskites have emerged as promising candidates for a multitude of optoelectronic technologies, owing to their versatile structure and electronic properties. The optical and electronic properties are harmoniously integrated with both the inorganic metal halide octahedral slab, and the organic spacer layer. The inorganic octahedral layers can also assemble into periodically stacked nanoplatelets, which are interconnected by the organic ammonium cation, resulting in the formation of a superlattice or superstructure. In this perspective, we explore the structural, electronic, and optical properties of lead-free hybrid halides, and the layered halide perovskite single crystals and nanostructures, expanding our understanding of the diverse applications enabled by these versatile structures. The optical properties of the layered halide perovskite single crystals and superlattices are a function of the organic spacer layer thickness, the metal center with either divalent or a combination of monovalent and trivalent cations, and the halide composition. The distinct absorption and emission features are guided by the structural deformation, electron–phonon coupling, and the polaronic effect. Among the diverse optoelectronic possibilities, we have focused on the photodetection capability of layered halide perovskite single crystals, and elucidated the descriptors such as excitonic band gap, effective mass, carrier mobility, Rashba splitting, and the spin texture that decides the direct component of the optical transitions.
