Self-assembly of polymeric materials into organized nano/microstructures has gained a considerable attention in nanoscience due to their versatile properties and morphologies, their relationship to biological structures, as well as their fundamental importance in many fields, such as biomedical, microelectronic, photoelectric and optical materials [1,2]. Among these, block copolymers with narrow polydispersities were widely used due to their excellent self-assembly behaviours [3], although the formation of assemblies in random copolymers is possible despite their indistinct structure caused by the broader dispersion arising from the random distribution of hydrophilic and hydrophobic segments throughout the polymer chains. Moreover, random polymers are readily synthesized (one-step copolymerization or one-pot post-polymerization treatment [4]) in comparison to block copolymers. Organized assemblies of different shape and size are obtained in solutions at a threshold concentration called critical aggregation concentration (CAC). Accordingly, a variety of poly(acrylamide)s and poly(methacrylamide)s containing different amino acids have been synthesized to study their structure and properties, as well as their characteristic polymerization behaviour [5]. The main processes that trigger their behaviour relies on the fact that these amphiphilic polymers undergo intra- or interpolymeric hydrophobic associations, that lead to the achieving of secondary structures in the form of micelle-like clusters, which show a higher compatibility with the biological systems, characteristic that can be exploited in the attaining of hydrophobically modified amino acidbased optically active polyelectrolytes. In this context, the aggregation behaviour of two types of random copolymers with D/Lphenylglycine moieties in the side chains was studied. The structures, thermal and optical properties of these polymers synthesized through free radical polymerization were investigated by spectral analyses (FT-IR, 1H NMR, 13C NMR), gel permeation chromatography, thermal analyses (TGA and DSC) and optical measurements. The self-assembly process can be monitored by using surface tension, fluorescence spectroscopy and transmission electron microscopy (TEM). The specific rotation values recorded for the two copolymers with dextro and levo enantiomeric forms have suggested a good correlation between the obtained experimental data, their direction of rotation being the same as in the starting monomers. The synthesized copolymers were explored in order to establish the potential applicability field of the polymeric aggregates.