A novel clay‐based polymeric nanocomposite was synthesized using alternative copolymer of ethyl vinyl ether and maleic anhydride. To this aim, first, montmorillonite (MMt) was modified by cetyltrimethyl ammonium bromide (CTAB) surfactant, and then in situ intercalative radical‐initiated copolymerization was performed. Different amounts of organo‐modified clay were used to determine its optimum amount in nanocomposite. The results showed that 2 wt% is the optimum amount of organo‐modified montmorillonite (OMMt) for nanocomposite preparation. Different characterization techniques including FT‐IR, XRD, SEM, UV‐Vis, DSC and TGA were used for characterization of prepared nanocomposites. The thermal behavior of nanocomposites measured by DSC and TGA techniques showed distinct increase in Tg and Tm of nanocomposites compared with pure copolymer. POLYM. COMPOS., 39:3889–3895, 2018. © 2017 Society of Plastics Engineers