This research intends to reduce the crystallinity of chitin with physical methods so as to improve the enzymatic hydrolysis efficiency of chitin. Scanning electron microscopy showed that both steam explosion and high‐pressure homogenization significantly enlarged the pores in shrimp shells, which are made up of chitin, but γ radiation did not. X‐ray diffraction showed that the crystallinity index of chitin decreased by 23.2% in the (110) plane and 24.7% in the (020) plane after three rounds of steam explosion and decreased by 12.4% in the (110) plane and 28.7% in the (020) plane after three rounds of high‐pressure homogenization. After γ radiation, however, there was no significant change. The corresponding deacetylation degrees of the chitin treated with steam explosion and high‐pressure homogenization increased by 13.2 and 5.7%, respectively. The natural, steam‐exploded and high‐pressure homogenized chitins respectively produced 0.251, 0.145, and 0.407 mg/ml reducing sugars with the hydrolysis of Streptomyces griseus chitinase. However, when hydrolyzed by Paenibacillus sp. A1 chitinase the steam‐exploded and the high‐pressure homogenized chitin respectively released 40 and 300% more reducing sugars than the natural chitin. The results found that steam explosion and high‐pressure homogenization can reduce the crystallinity of chitin, and make it prone to enzymatic hydrolysis.