<jats:p>Metal complexes with pyridine ligands (py) have not been crystallographically characterized in large numbers, while a large number of 2,2′-bipyridine (bpy) complexes have been structurally characterized. Against this background of scarcity of py complexes, the aim of this study was to characterize the structures and magnetic properties of complexes with pyridine ligands. In this study, new py complexes, trans-[Ni(H2O)2(py)4][BPh4]2·4py (1) and trans-[Co(H2O)2(py)4][BPh4]2·4py (2), were prepared and characterized by the single-crystal X-ray diffraction method and magnetic measurements. In the crystal structure analysis, both complexes were found to have octahedral trans-N2O4 coordination geometry, and the coordination of the trans-aqua ligands was found to be enhanced by the hydrogen-bonded pyridine molecules as a base. In the simultaneous analysis of magnetic susceptibility and magnetization, both complexes were found to show strong magnetism in one direction (χz > χx, χy; Mz > Mx, My), and this was explained by the enhancement of the axial aqua ligands. In the nickel(II) complex, the strong axial ligand field was found to cause negative zero-field splitting (D < 0) to show the magnetic behavior, while in the cobalt(II) complex, the strong axial π-orbital effect was found to cause negative ligand field splitting (Δ) in the 4T1 ground state to show the magnetic behavior.</jats:p>