The compound (Z)-2-(3-chlorophenyl)-N’-hydroxyacetamidine, (2) was synthesized and characterized by 1H NMR, FT-IR, TGA, UV-Visible Spectra, and elemental analysis. Its molecular structure was solved by single-crystal X-ray diffraction method. The title molecule, C8H9ClN2O is crystallized in the monoclinic crystal system with the space group P21/c and with unit cell parameters a = 8.7092(4) Å, b = 8.2370(4) Å, c = 12.5256(6) Å, β = 102.252(3)°, and Z = 4. The molecular and crystal structure of the title molecule is stabilized by an intramolecular interaction of the type N—HċċċO, and the intermolecular interactions of types N—HċċċN and O—HċċċN.