AbstractTwo new linear tri‐nickel(II) complexes with an infinite polymeric chain, [Ni3(μ3‐dpa)4(C4O4Me)](BF4)1and [Ni3(μ3‐dpa)4(N3)](PF6)2, [dpa−= di(α‐pyridyl)amido anion], have been synthesized and their structures were determined by X‐ray diffraction. Compound1crystallizes in the monoclinic system, space groupC2/c, witha= 19.9078(3),b= 13.2986(2),c= 37.6622(5) Å, β = 94.091(1)°, Z = 8. Compound2crystallizes in the monoclinic system, space group P 21/n, witha= 13.323(4),b= 23.217(3),c= 17.528(5) Å, β = 94.42(3)°, Z = 4. The two complexes are described as one‐dimensional systems with the (C4O4Me)−, 1, or N3−, 2, serving as a μ‐(1,3) bridged ligand at the two axial sites of each [Ni3(μ3‐dpa)4]2+fragment. The Ni‐Ni distances of 2.400(1) and 2.402(1) in1and 2.389(2), 2.385(2) in2are obviously shorter than those of 2.4325(7), 2.4356(7) in the monomeric complex [Ni3(μ3‐dpa)4(N3)2]3. The magnetic properties of complexes 2 and 3 were studied by susceptibility measurementsvstemperature. The χMvsT plots of both complexes show a strong antiferromagnetic behavior. The simulatedJ13values are −95 c