The aggregation‐induced emission (AIE) properties of a systematic series of naphthalene diimides (NDIs) varying the chain length at the imide positions have been studied. A solvophobic collapse of NDI units through the flash injection of THF NDI solutions in sonicating water triggers the formation of stable suspensions with enhanced fluorescence emissions. Shorter chains favor the π−π stacking of NDI units through H‐aggregation producing a strong AIE effect showing remarkably high quantum yields that have not been observed for non core‐substitued NDIs previously. On the other hand, NDIs functionalized with longer chains lead to more disordered domains where π−π stacking between NDI units is mainly given by J‐aggregation unfavoring the AIE effect.