Several novel derivatives of bis(N-1,2,4-diazaphosphol-1-yl)methane (bdpm) as well as the first bis(N-1,2,4-diazaphosphol-1-yl)methane metal complexes [Cu(bdpm)2(H2O)2]2+·2ClO4−, [(bdpm)Cu(μ-Cl)Cl]2, and [(bdpm)CoCl2] were prepared and structurally characterized. The complex [Cu(bdpm)2(H2O)2]2+·2ClO4− is with the higher local concentration of low-valent phosphorus(σ2λ3) on the periphery of the molecule. All compounds were characterized using 1H, 13C{1H}, 31P{1H} NMR, IR spectroscopy, and X-ray crystallography. The properties of compounds [Cu(bdpm)2(H2O)2]2+·2ClO4−, [Cu(bdpm)(μ-Cl)Cl], and [Co(bdpm)Cl2] were studied by the EPR spectroscopy and magnetic susceptibility.