High-entropy alloys (HEAs) present a vast compositional design space, characterized by four core effects—high configurational entropy, sluggish diffusion, severe lattice distortion, and the cocktail effect—which collectively underpin their exceptional potential for both structural and hydrogen storage applications. This mini-review synthesizes recent advances in the compositional design of HEAs with emphasis on structural materials and hydrogen storage. Firstly, it provides an overview of the definition of HEAs and the roles of principal alloying elements, then synthesizes solid solution formation rules based on representative descriptors—atomic size mismatch, electronegativity difference, valence electron concentration, mixing enthalpy, and mixing entropy—together with their applicability limits and common failure scenarios. A brief introduction is provided to the preparation methods of arc melting and powder metallurgy, which have a strong interaction with the composition. The design–structure–property links are then consolidated for structural materials (mechanical properties) and for hydrogen storage materials (hydrogen storage performance). Furthermore, the rules for the combined design of control systems for HEAs and the associated challenges were further discussed, and the future development prospects of HEAs in structural materials and hydrogen storage were also envisioned.

FeSiBAlNi (W5), FeSiBAlNiCo (W6-Co), and FeSiBAlNiGd (W6-Gd) high entropy alloys (HEAs) were prepared using a copper-mold casting method. Effects of Co and Gd additions combined with subsequent annealing on microstructures and magnetism were investigated. The as-cast W5 consists of BCC solid solution and FeSi-rich phase. The Gd addition induces the formation of body-centered cubic (BCC) and face-centered cubic (FCC) solid solutions for W6-Gd HEAs. Whereas, the as-cast W6-Co is composed of the FeSi-rich phase. During annealing, no new phases arise in the W6-Co HEA, indicating a good phase stability. The as-cast W5 has the highest hardness (1210 HV), which is mainly attributed to the strengthening effect of FeSi-rich phase evenly distributed in the solid solution matrix. The tested FeSiBAlNi-based HEAs possess soft magnetism. The saturated magnetization and remanence ratio of W6-Gd are distinctly enhanced from 10.93 emu/g to 62.78 emu/g and from 1.44% to 15.50% after the annealing treatment, respectively. The good magnetism of the as-annealed W6-Gd can be ascribed to the formation of Gd-oxides.