The single-crystal structure of neodymium chloride-ribopyranose pentahydrate, NdCl3·C5H10O5··5H2O was determined to have Mr=490.80, a=9.138(11), b=8.830(10), c=9.811(11) Å,β=94.087(18)°, V=789.7(16) Å3, P21, Z=2,μ=0.71073 Å and R=0.0198 for 2075 observed reflections. The ligand of the title complex was observed in a disordered state and two molecular configurations of NdCl3·C5H10O5 ·5H2O were found in the single crystal as a pair of isomers. Both ligand moieties of the two molecules are ribopyranose forms, providing three hydroxyl groups in ax-eq-ax orientation for coordination. One ligand of the pair of isomers is b-D-ribopyranose in the 1C4 conformation, and the other is a-D-ribopyranose in the 4C1 conformation. The Nd3+ion is nine-coordinated with five Nd-O bonds from water molecules, three Nd-O bonds from hydroxyl groups of the ribopyranose and one Nd /Cl bond from chlorideion. The hydroxyl groups, water molecules, chlorideions form an extensive hydrogen-bond network. The IR spectral C-C,O-H,C-O and C-O-H vibrations were observed to be shifted in the complex and the IR results are in accordance with those of X-ray spectroscopy.