To investigate hydrogen behaviors in the high-entropy alloy AlCrTiNiV, density functional theory and transition state theory were used to explore the molecular $H_2$ absorption and dissociation and the atomic H adsorption, diffusion, and penetration progress. The $H_2$ molecule, where the H-H band is parallel to the surface layer, is more inclined to absorb on the top site of the Ti atom site of first atomic layer on the AlCrTiNiV surface, then diffuse into the hollow sites, through the bridge site, after dissociating into two H atoms. Atomic H is more likely to be absorbed on the hollow site. The absorption capacity for atomic H on the surface tends to decline with the increase in H coverage. By calculating the energy barriers of atomic H penetration in AlCrTiNiV, it was indicated that lattice distortion may be one important factor that impacts the permeation rate of hydrogen. Our theory research suggests that high-entropy alloys have potential for use as a hydrogen resistant coating material.