Flow electrification occurs when a dielectric liquid flows along the wall surface, and it may cause electrostatic hazards such as spark discharges. Flow electrification issues of liquid hydrogen should be carefully treated since its low electrical conductivity and dangerous flammability. In this study, flow electrification characteristics of liquid hydrogen in pipe flow are numerically investigated. A theoretical model coupling the electric field and the flow field is introduced to govern the behaviour and distribution of charges, and an interface discharge model is adopted to describe the charge transfer boundary condition. The theoretical model is validated by comparing the simulation with experiment data, and the results show a good agreement with the averaged related deviation below 10%. The result of a common case, with flow velocity u of 1 m/s, pipe radius a 0.01 m, and length L 1 m, shows that the charge density, streaming current, and the electric potential of liquid hydrogen flow are in the magnitude of 10−12 C·m−3, 10−16 A and 10−2 V, respectively. Flow parameters, including flow velocity and pipe size, have a certain effect on the flow electrification characteristics of liquid hydrogen flow. By dimensionless parameterization, it is found that Reynolds numbers (Re), r/a, and x/a are exactly three orthogonal parameters determining the charge density distribution. Furthermore, the effects of electrical conductivity on the distribution of charges and charge dissipation have also been discussed. Finally, the safety assessment of the liquid hydrogen transportation system has been discussed, with extra consideration of the impurities and gas-liquid two-phase flow regime. To sum up, this work presents an in-depth and comprehensive insight into the flow electrification of liquid hydrogen flow, which is of great significance to the transportation safety of liquid hydrogen.