The threefold symmetric molecule, tris(4-cyanophenyl)amine (TCPA) is synthesized from 4-fluorocyanobenzene by treatment with potassium carbonate in dimethylsulfoxide; the occurrence of the reaction without any amine reagent suggests the involvement of a novel self-assembly process. A reprecipitation strategy provides stable colloids containing highly monodisperse nano/microcrystals with well-defined cubic morphology and sizes tunable from 250 to 500 nm. The solution, colloid, and solid states of TCPA exhibit strong blue fluorescence; the colloid shows dual emission with an unusually small Stokes shift. Computational investigations are carried out on the molecule and supramolecular assemblies derived from the crystal structure. Coupled with detailed spectroscopic studies, they show that the emission in the colloidal and solid states can be attributed to energy levels resulting from the intermolecular interactions within different aggregation motifs in the condensed phase and energy cascades between them. The computations also reveal the presence of cooperative interactions in the molecular crystal contributing to its high thermal stability. The strong light emission exhibited by TCPA, concurrently in the solution, nano/microcrystal, and solid states establishes it as a novel molecular material of potential practical utility; it has led to the exploration of the underlying mechanism that describes the phenomena observed in the different physical states.