We have investigated the dissolution, diffusion, and retention of hydrogen (H) in tungsten-rhenium (W-Re) sigma (sigma) phase using a first-principles method and thermodynamic models, in order to explore the influence of Re-rich precipitation on H behaviors in W. Taking the most stable W-Re sigma phase (W-33.3 at.% Re) as an example, it is found that the solution energy of H at most interstitial sites (>80%) in W-Re sigma phase is much lower than that in pure W. Specifically, the H solution energy at most stable interstitial site in W-Re sigma phase is only 0.47 eV, similar to 54% lower than that in pure W. This can be attributed to that W-Re sigma phase provides the larger available volume for interstitial H than the pure W, weakening the W-H repulsive interaction. Moreover, it has been demonstrated that this trend is almost independent on the Re concentration in W-Re sigma phase. We have further determined the interaction between H atoms and mono-vacancy in W-Re sigma phase based on the calculation of H trapping energies and the Polanyi-Wigner equation. The W-type and Retype vacancy can accommodate 10 and 5 H atoms at room temperature (RT) in a phase, respectively, and thus the average trapping capability of vacancy for H in sigma phase is stronger than that in pure W (similar to 6 H atoms at RT). Consequently, our calculations reveal that the Re-rich precipitation (both interstitial and vacancy sites) can serve as the strong trapping centers for H in W, significantly enhancing the H retention, which is entirely different from the negative effect of dispersed-Re/small Re clusters. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.