2,3-bis(2-pyridyl)-5,6-dihydropyrazine and a protonated phenanthroline (Phen) have been synthesized and the structure of protonated Phen is established by X-ray diffraction single crystal structure analysis. The coordination reactions of Phen, 2,2'- bipyridine and 2,3-bis(2-pyridyl)-5,6-dihydropyrazine with rare earth ions in low pH have been studied. The results show that 2,3-bis(2-pyridyl)-5,6-dihydropyrazine is hydrolyzed to be 2,2’-pyridil and protonated ethylenediamine. Meanwhile, Phen combines with proton, which results that nitrogen atoms can not coordinate with rare earth ions. The molecular formula of protonated Phen is C12H8N2HCl·H2O. It crystallizes in the triclinic space group P -1 (2), with a = 7.1212(14) Å, b = 7.2786(15) Å, c = 20.817(4) Å, α = 90.00º, β = 96.69(3) º, γ = 90.00 º, V = 1071.65(379) Å3, Z = 4.