The demand for high-performance aluminum components drives research into the design of novel alloys that can be processed by laser-based additive manufacturing. In recent years, the addition of grain refiners proved to be an effective strategy to reduce the hot-cracking of high-strength Al alloys. In this study, the solidification and aging behavior of an Al2139 alloy doped with additions of Zr and Ti for L-PBF was investigated. These elements favored the formation of a fine-grained structure free of cracks. The formation of Al₃(Zr,Ti) inoculants was predicted by Scheil simulations and observed as cuboidal particles in the center of α-Al grains. The microstructure of the as-built material featured fine and fully equiaxed grains, which appeared comparatively finer at the edge (300–600 nm) and coarser (0.8–2.0 μm) at the center of the molten pools. In both cases, there was evidence of Cu and Mg micro-segregations at the grain boundaries. The microhardness of 109.7 HV_0.5 in the as-built state was increased to 186.1 HV_0.5 after optimized T4 heat treatment, responsible for the precipitation of many rod-shaped Zr- and Ti-based second phases and quasi-spherical Cu-, Mn-, and Fe-rich particles. Prolonged exposure carried out to simulate high-temperature service caused a drop in microhardness and marked modification of the microstructure, evidenced by the rearrangement and subsequent spheroidization of Cu- and Mg-rich particles at the grain boundaries.