The influence of poly(vinyl alcohol) matrix on stereoregularity of replica polyacrylamide chains in matrix radical graft copolymerization process when varying the grafts number and molecular weight is studied by high-resolution. NMR spectroscopy. It was ascertained that the microstructure of formed polymer at homopolymerization and matrix copolymerization processes are not differed. H-1 NMR spectroscopy suggests a few contacts of graft chains with the main. chain through H-bonding intramolecular polymer-polymer complex forming in macromolecules of investigated poly(vinyl alcohol)-to-polyacrylamide graft copolymer.