We herein report a real-time optical reflectance/absorption study of the photochromic behavior of visible light absorbing (yellow) titania carried out using a newly designed novel accessory for a fluorescence spectrophotometer. Yellow rutile titania, thermochemically synthesized from technical grade titanium substrate, displays a fully reversible sequence of electronic processes controllable by optical reflectance/absorption photostimulated by UV or visible light; three absorption bands appeared in the range 2.16–1.52 eV that could be thermally annealed at temperatures up to 600 K. To carry out real-time studies of these processes, a special device was designed and constructed which when combined with the fluorescence spectrophotometer allowed for the measurement of the changes in the sample’s absorption, ΔAλ(t), at wavelength λ that corresponded to the maximum of the photoinduced absorption spectral bands under monochromatic light irradiation or temperature-programmed heating as well as light irradiation...