As an advanced near-net-shape processing method in which directly preformed, semi-finished products are created from liquid metals, spray forming has become popular in the development and application of new materials and is supporting industrialization. However, as investigated in this work, the problems of segregation and low hardness exist in the actual industrialization process, particularly for large-diameter M3 high-speed steel. It was here found that the annual ring segregation morphologies were mostly distributed from the edge to 1/2R, with a large number of stripes primarily enriched in C, Mo, and Cr elements, and the degree of segregation was mild. The ring segregation was located at the 1/2R position, where the main elemental enrichments were C, W, Mo, Cr, and V, and the segregation degree was severe. The formation of segregation during deposition is described based on an equilibrium solidification model. A slow cooling rate and heat dissipation from the surface to the inside were judged to be the main factors causing segregation and changes in the carbide morphology. In terms of hardness, with the increase in the quenching temperature to 1230 °C, the tempering hardness increased significantly. The analysis shows that a faster cooling rate in the atomization stage caused the solidified droplets to exhibit rapid solidification characteristics, and there was a higher proportion of MC carbide in the deposited billet. MC carbides cannot be fully dissolved using the conventional heat treatment process, which decreases the C, Cr, Mo, and V contents in the solution and, thus, reduces the secondary hardening capability. The findings show that, when the spray forming process is used to prepare large-diameter materials, it should not be considered a rapid solidification technology simply because of its atomization stage. Moreover, more attention should be paid to the influence of microstructure transformation during atomization and deposition.