The structural organization of extracted humic matter, polymeric or supramolecular, has been a long-standing controversial issue. In this paper, we show that the interaction between a reference humic material, the Suwannee River Humic Acid (SRHA), and a homologous series of cationic surfactants (n-alkyl trimethyl ammonium chloride) provides key insights to resolve the controversy. By combining measurements of turbidity, electrophoretic mobility, surface tension, and cryogenic transmission electron microscopy, we show that (i) the binding of cationic surfactant to the anionic humic acid is initially triggered by electrostatic interactions; (ii) the contrasting evolution of turbidity-surfactant concentration curves implies that the surfactant alkyl chain interacts with the hydrophobic moieties of humic matter from very low concentrations of surfactant; (iii) a drastic restructuring of humic matter occurs upon surfactant binding, which brings out supplementary anionic humic sites; (iv) in the presence of C12 cationic surfactant, SRHA spontaneously forms stable nanoscale unilamellar vesicles, which, in addition to the high surface activity of complexes, could be of interest in the remediation of oil-contaminated environments; (v) the sequence of molecular structures obtained from SRHA with increasing amounts of C12-cationic surfactant-humic-rich vesicles, aggregates, surfactant-rich vesicles-bears striking similarities with the phase behaviour of aqueous mixtures of anionic and cationic surfactants, thus supporting the supramolecular view of humic structure.