Ni-Cr-Si-Fe-B self-fluxing alloys are commonly used in hardfacing applications; in addition, they are subjected to conditions of wear, corrosion, and high temperatures, but are not used in casting applications. In this work, gravity casting is presented as a potential manufacturing route for these alloys. Three alloys with different chemical compositions were investigated with a focus on microstructure characterization, solidification path, and strengthening mechanisms. Phases and precipitates were characterized using a field emission scanning electron microscope employing energy-dispersive X-ray spectroscopy, wavelength dispersive spectroscopy, and electron backscatter diffraction. Nano- and microhardness indentations were performed at different phases to understand their contribution to the overall hardness of the studied alloys. Hardness measurements were performed at room temperature and high temperature (650 °C). The borides and carbides were the hardest phases in the microstructure, thus contributing significantly to the overall hardness of the alloys. Additional hardening was provided by the presence of hard Ni3B eutectics; however, there was also a small contribution from the solid solution hardening of the γ-Ni dendrites in the high-alloy-grade sample. The amount and size of the different phases and precipitates depended mainly on the contents of the Cr, C, and B of the alloy.