AbstractIn this paper, we report on an enhanced hydrogen permeation effect along grain boundaries in tungsten. Sputtered nanocolumnar tungsten layers (column lateral dimensions 100–150 nm and layer thickness 2 μm) were analysed by hydrogen permeation measurements in the temperature range 520–705 K. The experiments constitute a direct observation of this effect, previously postulated by means of a combination of indirect experiments and simulations and considered controversial due to the lack of direct measurements. DFT results support this observation since (i) the hydrogen binding energy to the grain boundary is 1.05 eV and (ii) the migration energies along the grain boundary and along the bulk are 0.12 eV and 0.20 eV, respectively. OKMC simulations, parametrized by DFT data, were used as a supporting tool to attain a better understanding of the involved phenomena. The OKMC results are also compatible with the observations. Indeed, they show that the fraction of hydrogen flux along grain boundaries in the steady-state permeation regime increases when decreasing the ratio of lateral dimensions to length of the nanocolumns, rapidly approaching unity when this ratio is < 2. Therefore, grain boundaries act as preferential migration pathways for H atoms at the studied temperature range in the studied samples. This behaviour has interesting implications to reduce the retention of hydrogen in several applications, in particular, fusion materials exposed to plasma discharges.