One Nd(III) complex [Nd3L3(OAc)(3)] (1) was synthesized from a conjugate Schiff base ligand H2L. It shows a chiral "triple-decker" structure (1.1 x 1.2 x 1.8 nm) with Nd(III) ions sandwiched between the Schiff base ligands. 1 exhibits NIR Nd(III) luminescence, and the LMET efficiency is calculated to be 13.8%. It displays high luminescence sensitivity and selectivity to Co(II). The K-SV value and LOD of 1 to Co(II) are 9.96 x 10(4) M-1 and 0.97 mu M, respectively.