A series of unsymmetric bimetal(II) (Fe, Co and Ni) complexes ligated by 2-methyl-2,4-bis(6-iminopyridin-2-yl)-1H-1,5-benzodiazepines were synthesized and characterized by IR spectra and elemental analysis, while a representative nickel(II) complex (5a) was determined by single-crystal X-ray crystallography. These iron(II) complexes were found to exhibit good activities for ethylene oligomerization and polymerization in the presence of MMAO and afforded α-olefins in high selectivity, and the composition of oligomers followed the Schluz–Flory distribution. The nickel(II) complexes mainly dimerize ethylene with considerable activity. The influences of coordinative ligands and reaction parameters were fully investigated on the catalytic activity and properties of these complexes.