Type V linerless hydrogen storage vessels made of all-composite face the challenges of cryogenic mechanical failure and hydrogen leakage of composites. The cryogenic mechanical performance and gas-barrier property of the carbon fiber reinforced polymer for Type V vessels are largely determined by the epoxy matrix. Carbon nanotubes are widely used as polymer reinforcement material to enhance the cryogenic mechanical performance and gas-barrier property of epoxy resins. In this work, multi-walled carbon nanotubes (MWCNTs) were dispersed into epoxy resins to prepare MWCNTs-modified epoxy resins. The cryogenic mechanical performance, gas-barrier and thermal properties of the modified resin were then investigated. The experimental findings revealed a 34.34% reduction in the gas permeability coefficient for the nanocomposites containing 0.9 wt% MWCNTs compared with the epoxy matrix. The tensile strength and failure strain at cryogenic temperature (77 K) experienced enhancements of 26.99% and 41.53%, respectively. In addition, the thermal stability and glass transition temperature of the modified resin were improved. As a result, the MWCNTs-modified epoxy resin exhibits improved gas-barrier property in addition to excellent cryogenic mechanical performance, making it ideal for manufacturing Type V linerless hydrogen storage vessels.