Display omitted •Through vacuum arc melting, a series of Cu doping Ti-Mn-based AB2-type alloys are obtained.•Cu doping enlarges the crystal cells of the alloys and increases the hydrogen storage capacity of the alloys.•The alloys with Cu doping can improve the activation performance, reduce hysteresis coefficient and optimize cycle life.•First-principles Simulations prove that Cu doping is beneficial to the hydrogen storage properties.•The introduction of Cu to optimize the properties of hydrogen storage alloys is universal. The Ti-Mn-based AB2-type hydrogen storage alloy has been widely researched and applied because of their higher hydrogen storage capacity, appropriate service temperature and low cost. However, before this hydrogen storage material becomes a mature technology, the essential issues of activation difficulty and high plateau pressure in hydrogen absorption/desorption process, need to be completely reformed by radical transformation in composition design and structure optimization. This work investigates the microstructure and hydrogen storage performances of Ti0.8Zr0.2Mn0.92Cr0.87Fe0.21 + x Cu (x = 0, 3, 5 and 8 wt%) by vacuum arc melting. Profiting from the excellent hydrogen transfer rate and structure optimization, the Ti0.8Zr0.2Mn0.92Cr0.87Fe0.21 alloys with the increasing of Cu doping result in the unique C14 Laves phase with the increased lattice volume. As a beneficial result, the decrease of the hydrogen absorption platform of Ti0.8Zr0.2Mn0.92Cr0.87Fe0.21 + 8 wt% Cu alloy is accompanied by the increase of the hydrogen desorption platform, thereby reducing the overall hysteresis coefficient of the material. Through Van't Hoff thermodynamic calculation results, it is found that the absolute values of hydrogenation enthalpy and entropy increase with the increasing of Cu doping. It is crucial to doping Cu inside the alloy by the accurate control of stoichiometric proportion and Cu content, which can improve the hydrogen storage performance of the alloy through theoretical analysis and First-principles simulation. This attempt enables new insights into the optimization of the hydrogen storage properties of Ti-Mn-based AB2-type hydrogen storage alloy, which can be generalized to the design of other new hydrogen storage materials.