In additive manufacturing, the flowability of feedstock particles determines the quality of the parts that are affected by different parameters, including the chemistry and morphology of the powders and particle size distribution. In this study, the microstructures and flowabilities of gas-atomized heat-resistant alloys for additive manufacturing applications are investigated. A KHR45A alloy powder with a composition of Fe-30Cr-40Mn-1.8Nb (wt.%) is fabricated using gas atomization process. The microstructure and effect of powder chemistry and morphology on the flow behavior are investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and revolution powder analysis. The results reveal the formation of spherical particles composed of single-phase FCC dendritic structures after gas atomization. SEM observations show variations in the microstructures of the powder particles with different size distributions. Elemental distribution maps, line scans, and high-resolution XPS results indicate the presence of a Si-rich oxide accompanied by Fe, Cr, and Nb metal oxides in the outer layer of the powders. The flowability behavior is found to be induced by the particle size distribution, which can be attributed to the interparticle interactions and friction of particles with different sizes.