High-purity epitaxial vanadium (001) films have been grown on magnesium oxide (001) and sapphire (1012BAR) at different substrate temperatures. X-ray diffraction, channeling, and high resolution transmission electron microscopy data prove the high structural perfection of these films. The residual resistance ratio (RRR) was measured to investigate the electrical transport properties of the vanadium layers. The experimental results for RRR depended on fabrication parameters and choice of substrate. A maximum value of RRR = 159 was obtained for vanadium on MgO. In addition, the superconducting transition temperature of the vanadium films was observed to depend systematically on layer thickness and residual resistance ratio.