Two high coordination crystals were obtained by the interaction of Ce~(3+) and Nd~(3+) with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis(2-pyridyl)dipyrazino[2,3-f:20,30-h]quinoxaline(HPDQ), and they were characterized. Complex 1 exhibits a 0 dimensional three-nuclear structure, with the three Ce(Ⅲ) atoms being ten-, eleven- and twelve-coordinated. Complex 2 is a 0 dimensional dual-core structure and the Nd(Ⅲ) atom is ten-coordinated. Complex 1 is of monoclinic system, space group P2/c with a = 16.850(3), b = 16.617(3), c = 24.017(5) ?, β = 100.94(3)o, V = 6602(2) ?~3, Z = 4, S = 1.062, F(000) = 3372, R = 0.0504 and wR = 0.1463(I > 2σ(I)). Complex 2 adopts a monoclinic system, space group C2/c with a = 25.795(5), b = 20.166(4), c = 13.059(3) ?, β = 112.29(3)°, V = 6286(2) ?~3, Z = 4, S = 1.004, F(000) = 2664, R = 0.0663 and wR = 0.1821(I > 2σ(I)). Furthermore, the behaviors of HPDQ with Ce~(3+) and Nd~(3+) in the solution are also investigated. After the Ce~(3+) is added, the ultraviolet absorption of the solution is enhanced with a red shift compared with that of the HPDQ ligand. While after adding Nd~(3+), the ultraviolet absorption of the solution is weakened, and it has a red shift which is the same as Ce~(3+). However, after the respective addition of metal ions, the emission of all solutions is quenched and has a red shift compared with that of the HPDQ ligand. Two high coordination crystals were obtained by the interaction of Ce ~ (3+) and Nd ~ (3+) with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis (2-pyridyl) dipyrazino [2,3 Complexes 1 exhibits a 0 dimensional three-nuclear structure, with the three Ce (Ⅲ) atoms being ten-, eleven- and twelve-coordinated. Complexes Complex 1 is a monoclinic system, space group P2 / c with a = 16.850 (3), b = 16.617 (3), c = 24.017 (5)?,? = 100.94 (3) o, V = 6602 (2)? ~ 3, Z = 4, S = 1.062, F (000) = 3372, R = 0.0504 and wR = 0.1463 Complex 2 adopts a monoclinic system, space group C2 / c with a = 25.795 (5), b = 20.166 (4), c = 13.059 (3) 6286 (2) ~ 3, Z = 4, S = 1.004, F (000) = 2664, R = 0.0663 and wR = 0.1821 (I> 2σ (I) +) and Nd ~ (3+) in the solution are also investigated. After the Ce ~ (3+) is add ed, the ultraviolet absorption of the solution is enhanced with a red shift compared with that of the HPDQ ligand. While after adding Nd ~ (3+), the ultraviolet absorption of the solution is weakened, and it has a red shift which is the same as Ce ~ (3+). However, after the respective addition of metal ions, the emission of all solutions is quenched and has a red shift compared with that of the HPDQ ligand.