Owing to the unique elemental character, Vanadium (V) has recently gained growing interest in the field of high entropy alloys. It is known that V benefits in the mechanical strength in alloys, accompanying by the unique elemental distribution behaviors. In this work, we concentrate on the mechanism of V's distribution characters in VFeCoNi, which is similar to that of Cr in CrFeCoNi, by evaluating element inherent electronegativity, charge transfer, atomic volume, Voronoi volume and the atomic stress resulting from the combined effects of these factors. Another unique character of electronic interaction in the t2g and eg orbitals has been observed, which contributed to the fluctuation of atomic volume, thus enhancing solid solution strengthening. The tensile stress-strain tests show that the chemical ordering of V enhanced mechanical strength, especially for the grain boundary. Our work will provide new insights into the nanoscale distribution of V elements and the related macroscopic mechanical effects.