The migration of plasticizers such as nitroglycerin seriously affects the storage and working safety of rocket systems. In this work, hydroxy-terminated polybutadiene (HTPB) liner composites with the cross-linked structure were prepared by cross-linking isocyanate functionalized graphene oxide (IGO) with HTPB to prevent the migration of high energy plasticizers in the propellant. IGO was uniformly dispersed in the matrix as reinforcement and cross-linker, providing good migration resistance and ablation resistance for the liner composites. Compared with pure HTPB, the migration resistance of the liner with 0.5 wt% IGO increased by 18.94%, 16.33% and 15.34% at 25 °C, 60 °C and 90 °C, respectively. In addition, the ablation resistance of the HTPB liner was improved by the addition of IGO. The improved anti-migration properties come from the special laminar structure of IGO and the dense molecular chains network of the cross-linked composites.