Here the composite polymer sorbent hydrogels were synthesized by in situ technique via free radical polymerization of acrylamide (AAm), 2-hydroxyethyl methacrylate (2HEMA) and N,N’-methylene-bis(acrylamide) crosslinker mixture in the presence of as-prepared dispersion of nickel-aluminum layered double hydroxide (NiAl-LDH). A content of active NiAl-LDH filler in the polymer matrix was varied in a range of 30 – 70 wt.%. It was found a high filler content suppresses a molecular mobility of copolymer matrix chains and reduces a beginning of glass transition temperature of the polymer constituent. The results of thermal analysis of polymer composites demonstrate a high hydrophilicity level of polymer matrix and high solvation energy of polar functionalities by Н2О molecules that was concluded from slow moisture elimination process while the temperature grows up to 200–210 оС. Additionally, a dehydration process and changes in a structure of thermally labile filler were also observed at the same temperature interval. At higher temperatures a thermal degradation of polymer poly(AAm-co-2HEMA) matrix is carried out. When a temperature overcomes 400 оС the partially changed filler demonstrates a chemical interaction with degraded organic constituents of the composites and defined catalytic activity as well. Studying sorption activity of the composites shown that introducing NiAl-LDH into hydrophilic polymer matrix provides anion-exchange activity to the composite sorbents and, correspondingly, the ability to eliminate the anionic contaminants from aqueous media while the polymer matrix doesn’t absorb these substances at such conditions. The highest sorption capacity of 11,40 μmol/g against model contaminant – methyl orange dye was determined for composite sorbent with filler content of 70 wt. %. At the same time sorption capacity of NiAl-LDH filler in composite sorbents reduces from 25,7 to 16,6 μmol/g while a filler content grows from 30 to 70 wt.% as a result of filler particles aggregation processes during composites formation stage. To evaluate the ability of the composite sorbents to reuse the experiment of materials recycling was performed. It was stated out the using of anion-exchange technique and aqueous Na2CO3 solution as an efficient and non-hazardous eluent provides 80 % recovering efficiency of the active filler in the composites. It can be concluded the composite sorbents demonstrate a high overall efficiency and are valuable materials for practical application for decontamination of waste water.