The intricate processes governing the gas atomization of molten metal droplets and their subsequent solidification hold paramount significance in materials science. Computational fluid dynamics simulations have emerged as indispensable tools for unraveling the complexities inherent in metal melt atomization. This study employed the volume of fluid method and the shear-stress transport k-ω turbulence model to simulate the primary atomization process of a FeCoNiCrMoBSi high-entropy alloy. Subsequently, the discrete phase model and Taylor analogy breakup model, based on the gas Weber number and incorporating primary atomization outcomes as initial conditions, were utilized to simulate droplet formation during the secondary atomization process. Analysis of the particle size distribution at the outlet of the geometric model demonstrated excellent agreement with experimental data for gas-atomized FeCoNiCrMoBSi high-entropy alloy powder. Furthermore, comprehensive characterization analyses were conducted to probe the phase constitution and structure of FeCoNiCrMoBSi powder produced by gas atomization. The results revealed that, irrespective of particle size, the powder exhibited a face-centered cubic structure and distinctive eutectic microstructural characteristics. The numerical simulation provided insights into the solidification process of secondary droplets by integrating inverse pole figure data for gas-atomized powder across varying particle sizes. The estimated cooling rate of secondary droplets ranged from 1.22 × 104 K/s to 2.64 × 105 K/s. These findings significantly advance the understanding of the gas atomization mechanism of the FeCoNiCrMoBSi high-entropy alloy, paving the way for the development of more efficient manufacturing processes for advanced materials.