This comprehensive review surveys developments over the past decade in the field of naphthalene diimides (NDIs). It explores their application toward: supramolecular chemistry; sensors; host-guest complexes for molecular switching devices, such as catenanes and rotaxanes; ion-channels by ligand gating; gelators for sensing aromatic systems; catalysis through anion-π interactions; and NDI intercalations with DNA for medicinal applications. We have also explored new designs, synthesis, and progress in the field of core-substituted naphthalene diimides (cNDIs), and their implications in areas such as artificial photosynthesis and solar cell technology. Also presented are some interesting synthetic routes and procedures that can be used toward further development of NDI-bearing compounds for future applications. Finally, we conclude with our views on NDI chemistry for future research endeavors, and we outline what we believe are the key obstacles that need to be overcome for NDIs to see real world applications.