The binuclear praseodymium(III) complex with N-(1-carboxyethylidene)-salicylhydrazide (C 10 H 10 N 2 O 4 , H 2 L) was prepared in H 2 O-C 2 H 5 OH mixed solution, and the crystal structure of [Pr 2 L 2 (HL) 2 (H 2 O) 4 ]•3H 2 O•C 6 H 6 was determined by X-ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P-1, and in the structure each Pr atom is 9-coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five-membered rings sharing one side in keto-mode and two water molecules. The coordination polyhedron around Pr 3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via µ 2 -bridging mode.