Herein, we investigate the dinuclearity effect of α‐diimine Ni‐based catalysts, N1 and N2 bearing different backbone on methyl methacrylate/1‐hexene (MM‐1H) copolymerization and characterize the copolymers microstructures using FT‐IR and NMR. The monomer reactivity ratio (r) is calculated using three different methods, a high reactivity ratio for MM (r1=9.9611), whereas a low reactivity ratio is obtained for 1H (r2=−0.0226). As determined by NMR analyses, up to 96 % of the MM incorporated into the main chain. Thermal copolymer properties are studied by DSC and TGA analyses, and the results are compared with those of Poly (methyl methacrylate) (PMMA). The higher content of MM in the copolymer backbone and the higher Tg for the copolymer samples (95.5 to 105.6 °C) were obtained. TGA shows that the degradation temperature of copolymers with higher 1H content progression reduced by about 10 % weight‐loss for N1 (327 to 240 °C) and N2 (325 to 236 °C). We are using a novel method with a low‐cost and speedy determination of polymer conductivity in both solid and liquid phases, which indicates the semi‐conductivity property of poly(MM‐1H) using corona discharges under the air atmosphere. Synthesized graphene‐poly(MM‐1H) nanocomposite shows the electrical conductivity augment from 3.45 μS of the poly(MM‐1H) to 30.42 μS for its nanocomposite.