Hypothesis: Organic radical polymers with tailored pendant functionalities have emerged as exciting and promising materials for their application versatility. Moreover, eco-friendly polymer-based organic nano materials with redox-active pendant side groups can replace the harmful heavy metal-based inorganic materials. On the other hand, self-assembled nanomaterials are of great interest and attracted more attention recently for their promising application in different advanced fields, but it is yet challenging to predict suitable hydrophilic-lipophilic balance (HLB) for stimuli-responsive random copolymers assembly due to structural irregularity. Among several experimental techniques, electron paramagnetic resonance (EPR) spectroscopy plays a unique and promising role in revealing structural and dynamic information of nanostructured radical containing materials. Experiments: In this study, a series of spin labeled amphiphilic random copolymers poly(methyl methacrylate-co-acrylic acid) have been synthesized and characterized by FT-IR, UV-Vis spectroscopies, TGA, DSC and water contact angle (CA) techniques. Their electrochemical properties have been determined by cyclic voltammetry (CV) in different organic solvents. EPR spectroscopy has been applied with other analytical techniques to elucidate the smart supramolecular nanoparticles (SNPs) formation, stimuli-responsiveness and structural changes through the dynamics of different molecular interactions. Findings: The structural and dynamic information of self-assembled nanoparticles have been observed to be dependent on multiple-stimuli-responsiveness in different microenvironments by applying physiolog-ical and chemical parameters such as the different concentration of radicals, pH, temperature, nature of the solvent and reducing agent. The obtained results reveal the knowledge to understand insight into the mechanism for the formation of stimuli-responsive colloidal nanoparticles assembled from amphiphilic random copolymers with apt HLB value. The CV results reveal that the charge transfer process of the nanoparticles in solution was diffusion regulated and depended on the accessibility of radicals. The radical (spin labeled) polymers offer a broad way to develop stimuli-responsive materials in various colloidal nanostructures by changing the microenvironment, appreciating their potential advanced applications in electronic devices, catalysis, stimuli-triggered drug/gene delivery and reactive oxygen species (ROS) scavenger. (C) 2020 Elsevier Inc. All rights reserved.