Effect of the alkyl chain and head-group of surfactant (monoisopropylolalkyl amines and diisopropylolalkyl amines) on its interaction with polymethacrylic acid in aqueous solution has been studied by surface tension, electrical conductivity and viscometric measurements. From the surface tension studies, the critical aggregation concentration and critical micelle concentration were determined. Depending on the nature of head-group and polymer concentration, the polymethacrylic acid-surfactant interaction and the character of variation of the colloidal-chemical parameters of the complexes were studied. Petroleum-collecting capacity of the obtained complexes has been estimated in the waters of various mineralization degrees. © 2017 Elsevier B.V.