Elemental powder blends are an emerging alternative to prealloyed powders for high-throughput alloy design via additive manufacturing techniques. Elemental Al+Sc(+Zr) powder blends were processed by laser powder bed fusion into Al-Sc and Al-Sc-Zr alloys, with operando X-ray diffraction at the Swiss Light Source extracting the structural and thermal history of the process. The pure Sc and Zr particles were found to react with the molten Al pool at 550–650 °C, well below their respective melting temperatures. Various scan areas (1 × 1, 2 × 2, 4 × 4, and 8 × 2 mm²) were studied to compare (i) the base plate "preheating" effect caused by prior laser scans, (ii) the return temperature reached after the melting scan and before the following scan, (iii) the initial cooling rate immediately after solidification, and (iv) the time spent in the "intrinsic heat treatment range", defined as 300–650 °C, where secondary Al₃(Sc,Zr) precipitation occurs. Microstructural analysis of the as-built samples show 110–140 nm L1₂-Al₃(Sc,Zr) primary precipitates at the bottom of the melt pool. The 1 × 1 mm² samples exhibit the most elongated grains (long axis of 10 ± 5 µm), which correlates with the highest build plate temperature and the slowest initial cooling rate (3–5 × 10⁵ K/s). In comparison, the 4 × 4 mm² samples exhibit the smallest equiaxed grains (2 ± 0.6 µm), corresponding to the lowest build plate temperature and the fastest initial cooling rate (6–7 × 10⁵ K/s). These results indicate the need for establishing a minimum feature size during part design, or for modifying the laser parameters during processing, to mitigate microstructure and performance differences across features of different sizes.