The atomic structure of a novel rare carth complex consisting of Nd and the sulfur-containing ligand pipdtc (C5H10NCS-2) has been studied with extended x-ray absorption fine structure (EXAFS) and x-ray diffraction techniques. The complex of formula Nd(pipdtc)4N(CH3)4 crystallizes in the monoclinic space group P21/n with the following lattice parameters, a = 22.685(2), b = 20.332(2), c = 17.1270(10)Å, β = 100.570(10)°, Z = 8. The calculated density is 1.47g/cm3. A new derivative method is used to remove, the post-edge absorption background including the multielectron excitation effect. The EXAFS results demonstrate that there are about eight S and four O atoms around Nd with the Nd-S bond length of 2.916 Å and the Nd-O bond length of 2.415 Å, respectively. This implies that the powder of this complex is not stable and is easy to oxidize in air. The possible change of structure before and after oxidation is discussed.