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This paper is dedicated to studying the effect of replacing molybdenum with vanadium on the tendency to amorphisation, structure, and thermal properties of high-entropy alloys of the (Fe0.25Ni0.25Co0.25Cr0.125Mo0.125‑xVx)100‑yBy system, where x = 0; 0.0625; 0.125 and y = 17–25. The alloy structure was analyzed using X‑ray diffraction, scanning and transmission electron microscopy methods. Thermal properties were determined by differential scanning calorimetry. It was found that the replacement of molybdenum with vanadium leads to the formation of crystalline particles of complex nitrides (V, Cr, Mo)(N, B) in the ribbon structure. The dependences of the characteristic alloy temperatures have been established. Molybdenum replacement with vanadium was shown to stabilize the supercooled liquid in alloys with completely amorphous structure. [ABSTRACT FROM AUTHOR]