We report on the effect of hydrogenation on sol–gel-derived, anatase-phase TiO2 nanoparticles. The structural analysis of white nanotitania (W-TiO2) and hydrogenated black titania (B-TiO2) has been carried out by X-ray diffraction (XRD) studies, which confirms anatase phase for both the cases, but with weak diffraction signals in the latter system. Upon hydrogenation, nanotitania system is believed to acquire a disordered phase in the form of a thin amorphous layer surrounding the nanoparticles, which can be realized through transmission electron microscopy analyses. As compared to W-TiO2 (~3.15 eV), the optical band gap of B-TiO2 is substantially reduced with respective band gap values of ~1.99 and 1.53 eV for 0.5 and 1 % H2 inclusion cases. Moreover, thermogravimetric analysis reveals high temperature thermal stability of B-TiO2 system, especially in the range of 350–600 °C. Exploiting thermal, optical and electronic properties of hydrogenated nanotitania could find scope in infrared optics, hydrogen storage and suitable photocatalytic applications.