The catalytic behaviour of polymer–surfactant (PS) composites has gained significant interest due to their ability to influence reaction kinetics through microenvironmental modulation. In this study, we explore the Ce(IV)-governed oxidative transformation of organic substrates in the presence of a polymer–surfactant composite composed of sodium dodecyl sulphate (SDS, 6 mM) and polyethylene glycol (PEG-600, 5 mM). Notably, the PS composite promotes the formation of premicellar aggregates at surfactant concentrations well below the critical micelle concentration (CMC), leading to enhanced reaction rates compared to systems involving the surfactant alone. The kinetics of the oxidation reaction were monitored via UV-Vis spectroscopy, revealing a pronounced rate enhancement attributed to the synergistic interaction between PEG-600 and SDS. The physicochemical characteristics and nature of the PS interaction were systematically investigated through tensiometry, dynamic light scattering (DLS), zeta potential measurements, nuclear magnetic resonance (NMR) spectroscopy, and field emission scanning electron microscopy (FESEM). These complementary techniques provide insight into the structural and dynamic aspects of the PS composites, elucidating its role in modulating the kinetics of Ce(IV)-catalysed oxidation pathway. This study underscores the potential of polymer–surfactant systems as tunable platform for catalytic applications in aqueous media.

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