Two complexes [Cd2(dpe)3(H2O)8]·(dpe)·(hssal)2·(H2O)2 1, [Mn(dpe)2(Hpcmb)2·(H2O)2] 2, (dpe = trans-1,2-di(4-pyrindyl)ethylene; H2hssal = sulphosalicylic acid; H2pcmb = p-(carboxyl-methyloxy)-benzenecarboxylic acid) has been prepared, and was characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structure indicates in complex 1 that Cd(II) is a distorted octahedral coordination geometry. The hssal2− anions are localized between 2-D sheets {[Cd(dpe)2(H2O)4]2+(dpe)}n and {{[Cd(dpe)2(H2O)4]2+}n as count anions and bridge to further connect these 2-D sheets through hydrogen bond O–H···O to form 3-D structure. The complex 2 is a single molecule structure. In 2, Each Mn(II) atom is six-coordinated with a distorted octahedral coordination geometry. The single molecule units are extended into three-dimensional structure via π–π, hydrogen bonding interactions. The thermogravimetric behavior and luminescent property of complex 1 were investigated. Two complexes, [Cd2(dpe)3(H2O)8]·(dpe)·(hssal)2·(H2O)2 1, [Mn(dpe)2(Hpcmb)2(H2O)2] 2 have been prepared, and were characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structures indicate that two complexes are extended into three-dimensional structure via π–π, C–H···π and hydrogen bonding interactions. The thermogravimetric behavior and luminescent property of complex 1 were investigated.