The zinc(II) complexes of taurine-vanillin and alanine-vanillin Schiff base were synthesized with taurine or L-alanine, and vanillin, zinc acetate and potassium hydroxide as main raw materials by one-step solid-solid reaction at room temperature. The composition and structure of the complexes were characterized by elemental analyses, molar conductance, Fourier transform infrared spectra (FTIR), X-ray powder diffraction (XRD), and thermogravimetry and differential scanning calorimetry (TG-DSC). The composition of complexes is [Zn(tau-van)(H2O)]·0.5H2O and [Zn(ala-van)(H2O)]·0.5H2O, and it is non-electrolytic nature. The experimental results indicate that the zinc ions are all four-coordinated by imino nitrogen, carboxylic oxygen or sulfonic oxygen and phenolic oxygen atoms from the Schiff base ligands, and oxygen atom from coordinated water molecule, respectively. The thermal decomposition processes of the zinc(II) complexes under air include dehydration and pyrolysis of the ligands, and the final residue is zinc oxide.