Nickel-based Ni-Cr-Si-B self-fluxing alloys are excellent candidates to replace cobalt-based alloys in aeronautical components. In this work, metal additive manufacturing by directed energy deposition using a laser beam (DED-LB, also known as LMD) and gas-atomized powders as a material feedstock is presented as a potential manufacturing route for the complex processing of these alloys. This research deals with the advanced material characterization of these alloys obtained by LMD and the study and understanding of their solidification paths and strengthening mechanisms. The as-built microstructure, the Vickers hardness at room temperature and at high temperatures, the nanoindentation hardness and elastic modulus of the main phases and precipitates, and the strengthening mechanisms were studied in bulk cylinders manufactured under different chemical composition grades and DED-LB/p process parameter sets (slow, normal, and fast deposition speeds), with the aim of determining the influence of the chemical composition in commercial Ni-Cr-Si-Fe-B alloys. The hardening of Ni-Cr-Si-Fe-B alloys obtained by LMD is a combination of the solid solution hardening of gamma nickel dendrites and eutectics and the contribution of the precipitation hardening of small chromium-rich carbides and hard borides evenly distributed in the as-built microstructure.