Abstarct: The Ligand N,N'-bis(2,6-dibenzhydryl-4-ethoxyphenyl)butane-2,3-diimine and the corresponding palladium(II) and nickel(II) baxsed α-diimine catalysts were synthesized via a multi-step reaction, and characterized. These LTM catalysts used in polymerization of ethylene. The structures of the both complexes were optimized, and the theoretical parameters were presented. The effects of reaction parameters such as polymerization temperature, co-catalyst to catalyst molar ratio and monomer pressure on the polymerization were investigated. Both of α-diimine catalysts demonstrated that to be thermally robust at high temperature about 90 °C. The highest activity of the nickel baxsed catalyst (494 kg PE/(mol cat.h) was obtained at [Al]/[Ni]=600:1, tp=90 °C and P= 5 bar. The highest activity of the palladium baxsed catalyst (330 kg PE/(mol cat.h) was also reached by 2 equivalent NaBAF (cocatalyst), tp=40 °C and P= 5 bar. Binary polymerization of ethylene was carried out using the nickel and the palladium baxsed complexes, and compared with corresponding individual of the catalytic systems. The average molecular weight, MWD of the binary polymerization was between the individual catalytic polymerization. The GPC analysis showed a narrow MWD 1.44 for the nickel baxsed catalyst, 1.83 for the palladium baxsed catalyst, and 1.61 for the binary catalyst system. However, the activity of the binary catalyst was lower than the two individual catalysts. The obtained polyethylenes have almost high molecular weights in the range of 1×105. The branching density of the polyethylenes generated by the binary catalytic system (30 branches/1000 C) is lower than of both the nickel baxsed (51/1000 C) and the palladium baxsed catalysts (40/1000 C). XRD study of the polymer chains showed higher crystallinity obtained in polymer samples with lowering branching. Also, FT-IR confirmed that all obtained polymers are a low density polyethylene (LDPE). In addition, the synthesized PE/MWCNT nanocomposite via in-situ polymerization showed the higher thermal stability (27 °C in presence of 3.88% MWCNT) than neat PE. The SEM investigation on the morphology of the samples, showed that the morphology of the palladium catalyst and related PE are virtually spherical according to replication phenomenon. The MWCNTs play the role of a bridge and an end-cap in the composite. However SEM images for the nickel baxsed catalyst and related PE demonstrated the amorphous structures for them. The morphology of obtained polyethylene by the binary catalyst system is the same as the both catalyst morphologies.