4 nm thick V layers grown by triode sputtering on MgO͑001͒ single crystals and capped with MgO exhibit a perfect epitaxy accompanied by a tetragonal distortion and an unexpected volume compression that increases with the V deposition temperature. The electrical resistivity follows a deposition temperature dependence with these structural modifications, decreasing by an order of magnitude across the temperature range studied. Total energy ab initio calculations rule out electronic structure changes and/or oxygen interface diffusion as responsible for the structure variation. Calculations of the ballistic conductance for the epitaxial V films do not reproduce the resistivity-volume correlation, implying a diffusive electron transport mechanism in the films, despite their high crystallinity. Instead, we assign the origin of the electrical behavior to the presence of growth induced defects in the V lattice, whose density is higher in films deposited at low temperature, and decreases as deposition temperature increases. These results extend the previous findings in volume expanded H loaded Fe/ V and Mo/ V superlattices to simpler structures where the H content is negligible and, additionaly, all the electronic transport is confined within the V film.