The resin suitable for the purification of esculetin from Viola tianshanica Maxim was selected from eight macroporous resins by static adsorption and desorption experiments, and its kinetics and thermodynamics behavior on compound was studied. The result indicated that HPD500 was the optimum material for the adsorption of esculetin. The adsorption dynamic behavior was well described by the pseudo-second-order kinetics equation. The adsorption isotherm data from the thermodynamics behavior were fitted better with Freundlich equation. The thermodynamic parameters were found to be ΔH<0, ΔS<0, and ΔG<0 respectively, so this adsorbing process was a spontaneous exothermic process. The optimal purification conditions of HPD500 on esculetin were as follows: loading concentration 2.593 5 mg/mL, maximum loading adsorption capacity 7.780 5 mg/g resin, adsorption rate 2.0 mL/min, 7 BV deimpurity water, 7 BV 50% ethanol elution, elution rate 2.0 mL/min. Under these conditions, the purity of esculetin was greater than 37% and the recovery rate was greater than 93.0%.