Nanocomposites with homogeneous dispersion of metal species have attained great attention due to their potential applications in various fields. Here, copper ion containing methacrylate copolymers were prepared by polymerization of copper methacrylate complex. The copper ion containing hybrid nanocomposite films were fabricated by layer-by-layer (LBL) assembly of copper ion containing methacrylate copolymers and transparent polyamic acid (PAA). LBL process was carried out with spin-assisted coating of PAA and dip-coating of copper ion containing methacrylate copolymers. The copper ion containing composite films were modified by thermal treatment and e-beam irradiation to reduce metal ions, resulting in higher mechanical properties. Modulus of modified copper metal-organic hybrid composite films was investigated by nano-indentation experiment.