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In this work, we present the synthesis and thermo-mechanical processing of a VMnFeCoNi high-entropy alloy. We outline the conditions required to obtain a homogeneous chemical composition and establish single-phase face-centered cubic and two-phase microstructures with different grain sizes. Vickers microhardness was systematically estimated to investigate the evolution of strength during thermo-mechanical processing and to determine how strength is affected by grain size. Our work shows that the annealing twin density of the alloy is quite low and therefore contributes minimally to grain boundary strengthening. Furthermore, VMnFeCoNi has relatively high Hall–Petch slope and intercept (infinite grain size strength) values in comparison to other well-documented high and medium-entropy alloys.