Supra-amphiphiles constituted of noncovalent bonds have emerged as attractive systems for fabrication of stimuli-responsive self-assembled nanostructures. A unique supra-molecular strategy utilizing halogen (X)-bonding interaction has been demonstrated for constructing emissive supra-pi-amphiphiles in water from a hydrophobic pyridyl functionalized naphthalene monoimide (NMI-Py) based X-bond acceptor and hydrophilic iodotetrafluorophenyl functionalized polyethylene glycol (PEG-I) or triethylene glycol (TEG-I) based X-bond donors, while their luminescent higher ordered assemblies were governed by orthogonal dipole-dipole interaction and pi-stacking of the NMI-Py fluorophore as probed by SCXRD and DFT calculations. Control molecules lacking iodotetrafluorophenyl moiety at the polyethylene glycol chain end failed to create any defined morphology from the NMI-Py, suggesting X-bonding is prerequisite for the nanostructure formation. Variation in the chain length of the X-bond donors leads to different morphologies (fiber vs vesicle) for PEG-I and TEG-I. Acid triggered denaturing of the X-bonds caused pH responsive disassembly of the thermally robust nanostructures. This strategy paves the way for facile fabrication of structurally diverse smart and adaptive luminescent functional materials with tunable morphology.