Vanadium-base alloys are expected as hydrogen separation materials because they have higher hydrogen permeability and good workability. In the present work, metallic vanadium thin films were prepared on sintered porous metallic substrates (stainless steel) by chemical vapor deposition (CVD) to approach the thermal expansion coefficient of films and substrates. CVD has several advantages such as direct forming the desired materials and facility of obtaining thin film. And, CVD is excellent for coating films on the porous substrates because of its relatively high deposition rate and superior step coverage. Vanadium oxytriethoxide was used as a vanadium source. It is organometallic compound, which has the advantage of using metallic films and substrates because of no chlorine. In addition, it is liquid and has a high vapor pressure. The films were deposited under controlled conditions, which were substrate temperatures, pressures of CVD chamber and flow rates of carrier gas (Ar) for source material. The size of substrate was 22 mm in diameter and 2 mm in thickness. The morphologies of films were observed by scanning electron microscope (SEM), and the elements in the films were investigated by energy dispersive X-ray spectroscope (EDX). The relation between the structures and CVD conditions, and the hydrogen permeability of films will be reported in a paper.