In the past three years, metal-free perovskites have garnered significant interest as promising candidates for utilization in next-generation wearable electronics. A variety of different molecular structures for these perovskites have been designed for different applications. However, there is still no systematic understanding that can elucidate the relationship between the structural details and properties of perovskites. This would provide a helpful guide for designing a metal-free perovskite with the desired packing structure and properties. Herein, we summarize recently reported structural and functional insights into metal-free perovskites. The underlying design of the molecular structure and its role in the packing structure and resulting properties are explained. In addition, important factors and challenges in the design of a molecular structure that will be useful for future applications are discussed. This information will help enrich the library of potential structures and future applications of metal-free perovskites, which is believed to be much larger than is currently known.