The diffusion reaction of 1,4-bis(1,2,4-triazol-1-yl)butane (btb) with Co(II)/Ni(II) ions as well as counter anions (PF6−) yielded two new coordination polymers, [Co1.5(btb)4.5](PF6)3 (1) and [Ni2(btb)6](PF6)4 (2). Both complexes have 3D uninodal 6-connected (412,63) net topology, forming triple interpenetrating structure. The distance between adjacent metal ions via btb bridging ligand is in the range of 13.930–14.181Å and 13.982–14.086Å, respectively. The magnetic behaviors of complexes 1 and 2 have been analyzed by one-ion approximation with spin–orbit coupling and zero-field splitting, respectively.