Reaction pathways to nitrogen- and fluorine-doped TiO₂ have been investigated and the compositions analyzed by neutron powder diffraction, nitrogen analyses and titrations of Ti³⁺. The reported formation of TiNF under pyrolysis of (NH₄)₂TiF₆ in NH₃ could not be reproduced when H₂O was carefully excluded. If special precautions are not taken to exclude H₂O, a product of the previously reported olive-green appearance is obtained; TiN_0.05O_1.89F_0.06, in which 1% of Ti is trivalent. The prolonged hydrolysis and ammonolysis leading to this product proceeds via the intermediates (NH₄)_1−xTiOF_3−x, which adopts the hexagonal tungsten–bronze structure, and/or TiOF₂. The latter is therefore suggested as a convenient starting material for doped anatase pigments. Reflectance measurements couple the green color with valence to conduction band excitations (E_g = 2.3 eV) and intraband transitions involving Ti³⁺. The green phase can be converted to a brilliant yellow in the presence of water vapor at 400–600 °C, which further hydrolyzes the fluoride and oxidizes the titanium, yielding TiN_0.04O_1.92F_0.04 in a particular case. The yellow color and band gap (E_g = 2.4 eV) may be promising for applications as a pigment or photocatalyst. Neutron powder diffraction characterizations and UV–Visible reflectance measurements indicate homogenous doping throughout the bulk. The combined results suggest that the green and yellow phases are part of a homogeneity range adjacent to TiO₂, in which the band gap narrowing results largely from nitrogen for oxygen subsitution and the green color is linked to formation of Ti³⁺ defects.