A new ligand, 4-dipropylaminobenzaldehyde thiosemicarbazone (abbreviated as HL), and its complexes ML2 (M = Ni, Pd, and Cu) have been synthesized and fully characterized by elemental analyses, EI-MS, IR and UVvis spectroscopy, and photoluminescence measurements. All of the compounds exhibit a bluegreen color with dual fluorescence in DMF solution. The quantum yield ratio (Φ′(CT)/Φ(LE)) decreases in the order NiL2 > HL > PdL2 > CuL2. The ligand HL crystallizes in the monoclinic system, space group P21/n, with a = 15.1680, b = 8.5573, and c = 25.3920 Å, β = 100.3457°, and V = 3242.2 Å3. The nickel complex (NiL2) crystallizes in the triclinic system, space group Pī, with a = 8.3093, b = 9.7540, and c = 10.2802 Å, α = 101.383°, β = 107.693°, γ = 96.703°, and V = 764.12 Å3. In these complexes, HL has lost a proton from its tautometric thiol form and acts as a single negatively charged bidentate ligand coordinating to the nickel ion via the mercapto sulfur and β-nitrogen atoms. The geometry around Ni(II) is almost square-planar with two equivalent NiN and two equivalent NiS bonds. The monomeric structure of HL or NiL2 is extended into an infinite two-dimensional network via hydrogen bonds. The two-photon absorption of HL and ML2 solutions (in DMF) was measured at 532 nm by the open-aperture Z-scan technique. Key words: crystal structure, metal complex, dual fluorescence, NLO.