AbstractRefractory complex concentrated alloys (RCCAs) show potential as the next-generation structural materials due to their superior strength in extreme environments. However, RCCAs processed by metal additive manufacturing (AM) typically suffer from process-related challenges surrounding laser material interaction defects and microstructure control. Multimodal in situ techniques (synchrotron X-ray imaging and diffraction and infrared imaging) and melt pool-level simulations were employed to understand rapid solidification pathways in two representative RCCAs: (i) multi-phase BCC + HCP Ti0.4Zr0.4Nb0.1Ta0.1 and (ii) single-phase BCC Ti0.486V0.375Cr0.111Ta0.028. As expected, laser material interaction defects followed similar systematic trends in process parameter space for both alloys. Additionally, both alloys formed a single-phase (BCC) microstructure after rapid solidification processing. However, significant differences in microstructure selection between these alloys were discovered, where Ti0.4Zr0.4Nb0.1Ta0.1 showed a mixture of equiaxed and columnar grains, while Ti0.486V0.375Cr0.111Ta0.028 was dominated by columnar growth. These behaviors were well described by the influence of undercooling effects on columnar-to-equiaxed transition (CET). Distinct microstructure formation in each alloy was verified through CET predictions via analytical melt pool simulations, which showed a ~ 5 × increase degrees in undercooling for Ti0.4Zr0.4Nb0.1Ta0.1 compared to Ti0.486V0.375Cr0.111Ta0.028. Overall, these results show that microstructure control based on modulating the freezing range must be balanced with process considerations which resist defect formation, such as solidification crack formation in RCCAs. Graphical abstract