We describe the growth and properties of well-defined epitaxial TiO 2− x N x rutile for the first time. A mixed beam of atomic N and O radicals was prepared in an electron cyclotron resonance plasma source and Ti was supplied from a high-temperature effusion cell or an electron beam evaporator, depending on the required flux. A very high degree of structural quality is generally observed for films grown under optimized anion-rich conditions. N substitutes for O in the lattice, but only at the ∼1 at.% level, and is present as N 3−. Epitaxial growth of TiO 2 and TiO 2− x N x rutile prepared under anion-rich conditions is accompanied by Ti indiffusion, leading to interstitial Ti (Ti i ), which is a shallow donor in rutile. Our data strongly suggest that Ti i donor electrons compensate holes associated with substitutional N 2− (i.e., Ti(III) + N 2− → Ti(IV) + N 3−), leading to highly resistive or weakly n-type, but not p-type material. Ti 2p core-level line shape analysis reveals hybridization of N and Ti, as expected for substitutional N. Ti–N hybridized states fall in the gap just above the VBM, and extend the optical absorption well into the visible.