Tetraphenylethene-core-substituted naphthalene diimide (TTPEcNDI) shows distinct near-IR optical properties and aggregation induced emission phenomena. Furthermore, TTPEcNDI aggregated into a variety of supramolecular assembled structures via solvophobic control such as hollow spheres, bundles of fibrils and leaf-like structures with controlled dimensions. The present study can be applied to more elaborate supramolecular structures for the development of near-IR solid emitter luminescent nanomaterials for electronic applications.