Abstract: Baicalin solution and the mixed solution of baicalin and chromium ions were titrated respectively by a certain concentration of potassium hydroxide solution in the constant temperature titration system, and the pH value of the solution was determined by the data acquisition software recording the reaction process. The stepwise conditional stability constants of Cr(Ⅲ)-complexes with baicalin were calculated by the method of generating function intercept:lgK₁=8.36,lgK₂=6.90, and the distributions of the complex species were calculated under different pH value.