Acrylamide‐vinyl alcohol (AAm/VA) graft copolymer was prepared and characterized. The interaction of the graft copolymer with poly‐(methacrylic acid) (PMAA) in water was studied by several experimental techniques, such as viscometry, potentiometry, conductometry, IR spectra, and transmittance measurements.PMAAwas found to interact with the graft copolymer in two distinct steps. The relative complexation ability of PAAm andPVAwith respect toPMAAdoes not change when these polymers are present as parts of a graft copolymer chain.