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) A, beta=94.087(18) degrees, V=789.7(16) A3, P2(1), Z=2, mu=0.71073 A 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 beta-D-ribopyranose in the 1C4 conformation, and the other is alpha-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 chloride ion. The hydroxyl groups, water molecules, chloride ions 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.