The electronic and magnetic structures of Fe–V alloys are calculated using the discrete-variational and full-potential linearized-augmented-plane wave methods. The derived hyperfine properties at Fe sites are studied against the number of Fe atoms in the neighbouring shells. As expected the magnetic hyperfine field depends strongly on the number of Fe atoms in the first and second shells of neighbours while its dependence on the variation of atoms in the third shell is weak. The calculated distribution of the magnetic hyperfine fields at the Fe sites, are compared to the experimental data of Krause et al. (Phys Rev B 61:6196–6204, 2000). The contact charge densities and the magnetic moments are also calculated. It was found that the contact charge density increases with increasing V contents and this leads to negative isomer shift on addition of V.