The title compound [Zn(C10H9NO5S)(C12H8N2)(H2O)]·4.25H2O (1) (where H2 (C10H9NO5S) = 2-[(5-formyl-salicylic)-amino]-ethanesulfonic acid, C12H8N2 = Phen), has been synthesized and characterized by IR, elemental analysis, and X-ray diffraction analysis. The crystal of the compound belongs to the triclinic system, space group P-1. The complex is a = 13.830(3), b = 14.704(2), c = 15.474(2) Å; α = 106.680(10)°, β = 102.580(10)°, γ = 114.100(10)°; S = 1.051; V = 2541.6(7) Å3; Z = 2; Dc = 1.556 g/cm3; F(000) = 1234; μ = 1.110 mm−1; R 1 = 0.0577, wR 2 = 0.1561. According to the structural analysis, the crystal structure of (1) is the transition metal complex of Schiff base derived from taurine and 5-formylsalicylaldehyde. The central Zn(II) cation was six-coordinated with two O atoms, one N atom of the ligand (C10H9NO5S), two N atoms of phen, and one O atom of the coordinated water to form a slightly distorted octahedron structure. There are two complex molecules in one asymmetric unit, this two molecules were linked by hydrogen bonds and π–π stacking between the two aromatic rings. The netlike structure was assembled by many intramolecular and intermolecular hydrogen bonds and π–π stacks.