Nine mixed-ligand Cd2+ complexes of [Cd(Hdmpz)2(bcaa)2] (1) (Hbcaa = 3-(benzylcarbamoyl)-acrylic acid), Cd4(Hdmpz)4(tcba)8(2) (Htcba = 2,4,6-trichlorobenzoic acid), [Cd(Hdmpz)(napa)2] (3) (Hnapa = 1-naphthoic acid), [Cd(Hdmpz)2(cnba2] (4) (Hcnba = 2-chloro-4-nitrobenzoic acid), Cd(Hdmpz)2(hmba)2 · H2O (5) (Hhmba = 4-hydroxy-3-methoxybenzoic acid), [Cd(Hdmpz)2(msal)2] (6) (Hmsal = 3-methylsalicylic acid), [Cd(Hdmpz)2(dbta)(H2O)] · 2H2O (7) (H2dbta = dibenzoyltartaric acid), [Cd(Hdmpz)4(tpda)] (8) (H2tpda = 2,5-thiophenedicarboxylic acid) and [Cd3(Hdmpz)6(btca)2(H2O)4] · 2H2O (9) (H3btca = 1,2,4-benzenetricarboxylic acid) were synthesized and formulated by EA, IR spectra + SCXRD, their TGA were also conducted.The SCXRD reports indicated that the complexes exhibit mononuclear to tetranuclear structures with octahedral geometry at the Cd2+. The Hdmpzs in all examples are coordinated only through the monodentate fashion with its neutral N. The carboxylate at 8 displays only as unidentate coordination, while the ones in 1, 4 and 5–7 take the chelating bidentate coordination mode. The CO2− at 2–3 adopts both the chelating bridging tridentate and bismonodentate coordination fashion. 9 contains both unidentate and bidentate chelating coordinate CO2−. There all existed the NH···O H-bond from the NH of the Hdmpz. 6 has the intramolecular OH···O H-bond from the ortho phenol and the CO2−, resulting the S11(6) pattern. 5, 7 and 9 have the intermolecular OH···O H-bond. 2, and 4–6 bear only the intermolecular NH···O H-bond; 3, and 8–9 have only the intramolecular NH···O H-bond. Compounds 1 and 7 bear both the intra- and intermolecular NH···O H-bonds.There featured intricate intra- and intermolecular classical H-bonds (NH···O/OH···O) together with CH-π/CH2-π/CH3-π, CH3-CH/CH3-CH3, CH3-C, CH-O/CH3-O, CH-Cl/CH3-Cl, Cl-O, Cl-π, O-π, OC plus OO associates which are illuminated by the X-ray crystallographic technique, tethering the discrete units into high-dimensional ordered supramolecular systems.