The paper concerns the optimal process for extracting polysaccharide from bamboo shoot shells by using the multi-enzyme method. The extraction rate was selected as an indicator for the evaluation of antioxidant activity of polysaccharide. Single factor tests were carried out and the optimum process conditions, such as the optimal enzyme concentration, enzymatic time and temperature, were acquired by using the response surface methodology. The extracted polysaccharide was purified with Sevag reagent, and its monosaccharide composition and antioxidant activity were studied. The results show that the optimal process parameters are as follows: enzyme concentration 1.6%, enzymatic time 105 min, enzymatic temperature 51 ℃. The extraction rate of polysaccharide under the optimal conditions is 1.98%, and the average relative error between the experimental and predicted values is 2.94%. The mole ratio among the main monosaccharide composition, including the galacturonic acid, galactose, xylose and Arabia sugar is 15.35 ∶ 32.82 ∶ 6.45 ∶ 39.13. The purified polysaccharide extracted from bamboo shoot shells has good antioxidant activity, and the ability of scavenging DPPH radicals and hydroxyl radicals is of a certain concentration dependence.