The deuterated tris(hexafluoroacetylacetonato)neodymium(III) complex, Nd(HFA-D)(3), was obtained by ketoenol tautomerism reaction of Nd(HFA)3 in methanol-d(4). The emission of Nd(HFA-D)3 was observed in the following anhydrous deuterated organic solvents : methanol-d(4), acetone-d(6), THF-d(8), DMF-d(7), and DMSO-d(6). The intensity and lifetime of the emission in DMSO-d(6) are much superior to those in other deuterated solvents. The specific interaction of DMSO molecules with Nd(HFA)3 was confirmed by C-13 NMR and F-19 NMR analysis. The strong coordination ability of DMSO to Nd3+ ion in Nd(HFA-D)(3) led to the enhanced emission in DMSO owing to the suppression radiationless transition via vibrational excitation of D2O molecules in the vicinity of Nd(HFA-D)(3).