Gas atomization is a widely used method to produce the raw powder materials for additive manufacturing (AM) usage. After the metal alloy is melted to fusion, gas atomization involves two relatively independent processes: liquid breakup and droplet solidification. In this paper, the solidification behavior of powder during solidification is analyzed by testing the powder’s properties and observing microstructure of a martensitic stainless steel (FeCrNiBSiNb). The powder prepared by gas atomization has high sphericity and smooth surface, and the yield of qualified fine powder is 35%.The powder has typical rapid solidification structure. Collision between powders not only promotes nucleation, but also produces more satellite powder. The segregation of elements in powder is smaller as the result of high cooling rate which can reaches 4.2 × 105 K/s in average. Overall, the powder prepared by gas atomization is found to have good comprehensive properties, desired microstructure, and accurate chemical component, and it is suitable for various additive manufacturing techniques.