The applications of nano-dispersed organic conjugated active compounds or materials as well as current research is concerned mainly with optimization and control of the optical properties, by particle size and supramolecular structure of the particles. The aromatic macromolecules consisting of conjugated rigid rod segment and hydrophilic flexible chain as coil in aqueous solution can aggregate into a variety of supramolecular structures through mutual interaction between aromatic rod and hydrophilic chains of molecules and water. Here we report the synthesis of newer oligo phenylene vinylene (OPV) based rod-coil molecules with varying chain-length polyethylene oxide (PEO) repeating units (n = 8, 17, 45). Formation and photophysical properties of their nanostructures in water are studied comparatively. The nanostructures evolution of these molecules is observed with simple reprecipitation method. The stable nanostructures were formed without addition of any surfactants. The fabricated nanostructures ultimately give the materials with ‘controlled’ aggregation induced enhanced photophysical properties. The self-assembly of such OPV type rod molecules in water without adding any surfactants, therefore, can provide a strategy for the construction of well-defined and stable nanostructures with certain chemical functionalities and physical properties as advanced materials for photonic, electronic and biological applications. Copyright © VBRI Press.