Here, the storage sites of hydrogen in FeCr alloy, namely (H, He)-V nano-clusters with open volume, have been investigated by first-principles calculations and positron annihilation spectroscopy. The positron lifetimes in the nano-clusters obtained by theoretical calculations and experiments were compared. These results suggest that positron is sensitive to the relative position of the gas atoms decorating the open volume; and a helium atom forms a more repulsive ion core than a hydrogen atom when it occupies the vacancy, resulting in a decrease in positron lifetime. Interpretation of the PAS data was successfully combined with theoretical calculations, and allowed us to determine the defect status in specimens after H/He irradiation with different implantation patterns. The speculated kinds of hydrogen storage sites formed after irradiation are summarized. For the He-ions pre-implanted situation, the helium-vacancy clusters or bubbles forming in advance may recombine with H atoms to form stable He-H-V complex. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.