The title compound, bromo-(2-diphenylphosphino-N-(2-oxybenzylidene)-aniline)-nickel, was synthesized by simple condensation of 2-diphenylphosphino-N-(2-oxybenzylidene)-aniline with NiBr 2 ·6H 2 O and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 9.756(2), b = 10.232(2), c = 13.313(3) Å, α = 95.09(3), β = 102.48(3), γ = 95.45(3)º, V = 1283.5(4) Å 3 , C 29 H 23 BrNNiO 2 P, M r = 587.07, Z = 2, D c = 1.519 g/cm 3 , λ(MoKα) = 0.71073 Å, F(000) = 596 and µ = 2.402 mm -1 . The structure was refined to the final R = 0.0408 and wR = 0.0965 for 4507 observed reflections (I > 2σ(I)). Intermolecular π-π interactions (with distances of about 3.705 Å) are pronounced in the crystal structure. Under methylaluminoxane (MAO) activation, the title com-pound was able to catalyze norbornene polymerization, exhibiting good polymerization activities.