Supramolecular well-defined nano-microstructures are grown much interest in both scientific and technological interest due to their applications in nano- and bio-techalogical research. In this report, we described synthesis of amphiphilic naphthalenediimide (NDI) derivative (1) bearing melamine (MM) head group and studied its self-assembly with solvophobic control. Interestingly, derivative 1 produces well-defined flower-like supramolecular structure in THF/hexane solvent mixture. Furthermore, SEM imaging used to visulaise step-wise growth of flower-like assembly. The formation of flower-like supramolecular assembly is attributed to π-π stacking of the NDI core, along with hydrophobic interactions of an alkyl chain along with H-bonding of the melamine head group. We believe such arrangement within the molecule prevent crystalisation and favour the directional growth of flower-like streuctures. The self-assembled flowers exhibit porous structures similar to natural flowers, and may find practical applications in the field of optoelectronic materials, mimicking enzyme catalysis and biosensors.