A novel zinc complex (ZnE) has been designed and synthesized based on the derivative of 2-(2΄-hydroxyphenyl)-1-H-benzimidazole (HBI) and the neutral nitrogen-containing ligand (phen). The crystal of the title complex crystallizes in the monoclinic system, space group P2₁/n with a = 10.2631(2), b = 34.2166(6), c = 11.4103(3) Å, β = 96.771(2)°, M_r = 844.24, V = 3978.99(14) ų, Z = 4, the final R = 0.0400 and wR = 0.1001 for 8107 observed reflections (I > 2σ(I)). In the title complex, the free protonated phenoxide moiety (4-OH) is successfully retained to realize pseudo-intramolecular hydrogen bonds with the coordinated O atom from the other ligand.