The manufacturability of equiatomic high-entropy alloy (HEA) particles with single- and dual-phase crystal structures using the high-energy mechanical alloying (HE-MA) method was explored in this study. Following a material design-of-experiment (DoE) curriculum, particles were synthesized in a planetary mill. Milling times varied while operating under two distinct HE-MA manufacturing regimes: the conventional approach (simultaneous milling of constituent elements) and the sequential method (progressive milling with the introduction of elements in a specific order). Within the conventional regime, equiatomic AlCoCrFe and AlCoCrFeNi blends were milled, focusing on the influence of incorporating nickel (Ni) as a transient element into the base composition. This led to an equivalent particle size distribution ranging from 5 to 100 μm. Notably, the presence of Ni resulted in an increased fraction of the face-centered cubic (FCC) phase, coupled with a simultaneous reduction in grain and crystallite sizes, thereby enhancing the overall material strength. This knowledge was applied to the design and synthesis of a target equiatomic FeNiCoCrAl HEA system. In this context, individual elements were added to the starting/milled Fe + Ni alloy at four-hour intervals, in line with the sequential milling regimen. The results showed an interesting evolution: the conventionally milled AlCoCrFeNi particles exhibited a dual-phase body-centered cubic (BCC) and FCC structure, with a composition of 55% BCC and 45% FCC phase fractions, while the sequentially milled FeNiCoCrAl particles demonstrated a single-phase BCC structure after 24 h of milling.