Methanol–water system possesses unusual interactions, which may affect surfactant self‐assembly. The main objective of this study was to investigate the interactions and aggregation behavior of ionic surfactants sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) and their equimolar catanionic binary mixtures (CAM) and their ternary mixtures with poly(ethylene oxide) (PEO) in aqueous solutions containing different volume percentages of methanol. Conductometry, surface tensiometry, and dynamic light scattering were employed for this purpose. The aggregation in all the systems showed methanol‐dependent patterns. The maximum shifts observed in the critical aggregation concentrations were 5.5, 2.7, 6.3, 4.1, and 4.4 mM, respectively, for SDS, CTAB, CAM, SDS/PEO, and CTAB/PEO systems for variation in MeOH from 5% to 30% v/v. The change in dielectric of the media and chaotropic nature of methanol was responsible for alteration in self‐assembly. The nature of surfactant especially and head group hydrophobicity also played a significant role in the process. The maximum change in area per molecule (i.e., ~4 nm2) occurred for CTAB/PEO system. The aggregation was delayed in surfactant solutions; however, the presence of polymer induced aggregation due to favorable polymer–surfactant interactions involving the surfactant adsorption onto polymer chains and formation of mixed aggregates. The hydrodynamic radii for CTAB/PEO systems, which were nearly 10 times greater than those recorded for SDS/PEO, showed the transition of system to nonspherical aggregated states. In short, the presence of methanol retarded the aggregation in surfactant and surfactant–polymer systems.