The diffusion behavior of substrate element into a deposited film was investigated. The observed systems were a Nb film/Ti substrate and a Ti film/Nb substrate. When the Nb film/Ti substrate was heated in a vacuum, Ti diffused very rapidly in the Nb film. The pre-exponential factor of the diffusion constant of Ti in the Nb film was 5.6 × 10-2 mMIN2 s-1, and the activation energy was 220 kJmol-1. The observed activation energy is about 60% of that of Ti in the bulk Nb. On the other hand, when the Ti film/Nb substrate was heated in a vacuum, Nb did not diffuse so rapidly. Titanium diffused through the Nb film rapidly and was concentrated on the surface of the Nb film. The chemical state of the concentrated Ti was metallic, and neither titanium oxides nor titanium carbide was observed. Therefore, the driving force of the rapid diffusion of Ti in the Nb film is considered as the reduction of the surface energy of Nb film. The difference in the diffusion behavior between Ti through the Nb film and Nb through the Ti film is explained supposing that the segregation of Ti reduces the surface energy on the Nb film but the segregation of Nb does not reduce the surface energy of the Ti film. After heating of the Nb film/Ti substrate for a long time, a new phase was formed at the interface between the Nb film and the Ti substrate. The chemical composition of the new phase is about 50% of Ti and 50% of Nb. This phase has not been reported in the phase diagram of the bulk Ti-Nb system. The surface area of the Nb film is considered to be quite large, so the contribution of surface energy to the thermodynamic state of the Nb film cannot be neglected. Therefore, the chemical potential of the film is different from that of the bulk. Then, the new phase, which does not exist in the phase diagram of the bulk system, is formed by an interaction of the films.