AbstractThe X‐ray absorption K‐edge spectrum of titanium in (Ti, Nb)O2, rutile or pseudo‐rutile solid solutions is recorded. The second derivative spectra are used to measure the energy shift of the transitions. A partial transfer of Nb 4d electron onto Ti 3d orbitals is found implying a similar energy of these orbitals. On the other hand a decrease of the crystal field is observed when Nb content increases. This may arise from the increase of the mean number of conduction electrons or the increase of the mean size of the metallic octahedron. Lastly, because the electronic structure of the titanium evolves continuously with the niobium content, niobium is certainly randomly distributed around the tit