Five new complexes [Zn(HL₁)(OAc)(CH₃CH₂OH)] (1), [Cd₂(HL₁)₂(OAc)₂(CH₃CH₂OH)₂] (2), [Cu₆(L₁)₆] (3) (H₂L₁ = N-(1-phenyl-3-phenmethyl-4-phenylethylene-pyrazolone-5)-salicylidene hydrazide, OAc = acetate anion), {[Zn(L₂)(CH₃OH)]·(CH₃OH)}_n (4) (H₂L₂ = N-(1-phenyl-3-phenmethyl-4-ethylene-pyrazolone-5)-salicylidene hydrazine), [Cu(L₃)]_n (5) (H₂L₃ = N-(1-phenyl-3-phenmethyl-4-benzylidene-pyrazolone-5)-salicylidene hydrazide) have been synthesized and characterized by chemical and spectroscopic techniques. Complexes 1–3 feature mononuclear, dinuclear and rare hexanuclear structures, respectively. The different molecular structures and different coordination modes of H₂L₁ in complexes 1–3 indicate that the coordination geometry of the metal atoms have a remarkable impact on the structure of these complexes. Complexes 4 and 5 have 1D chain structures. Comparing complexes 4 and 1 or 5 and 3, it can be concluded that the substituents at the 4-position of the ligands have a significant effect on the structure of the resulting complexes. It is worth noting that N(2) atoms of the pyrazolyl ring play an important role in building the two-dimensional networks for 1 and 2 by hydrogen bonds, a novel hexanuclear unit for 3, and the 1D polymer chain for 4 and 5 by bridging bonds. Complexes 1, 2 and 4 show strong fluorescent behavior in the solid state. The magnetic property of complex 3 shows the presence of intramolecular antiferromagnetic exchange (J = −8.63 cm⁻¹).