In this study, a detailed assessment of interactional conduct between different head-groups of cationic surfactants and different monomer fragments of anionic polyelectrolyte of aqueous media is reported. Tensiometry, conductometry, viscosimetry, dynamic light scattering have been employed to get insight into interactions among cationic surfactant and polyelectrolyte in interfacial region critical aggregation and micellization concentration, surface excess concentration, surface pressure at interface, minimum area occupied with the aid of one molecule of cationic surfactant at air-solvent interface, adsorption efficiency, surface tension at critical micelle concentration and the positive degree of counterion binding had been calculated. Thermodynamic parameters, i.e., standard Gibbs free energy of micellization and adsorption processes had been evaluated. Polyelectrolyte-surfactant interaction used to be studied in dependence on nature of head-group of cationic surfactant and polyelectrolyte chain and their influence on colloidal-chemical parameters of polyelectrolyte-surfactant complexes has been compared. Petrocollecting ability of these complexes in the waters of various mineralization degree was investigated. © 2020 Elsevier B.V.