High-concentration niobium (V)-doped titanium dioxide (TiO2) nanoparticles of the nonequilibrium chemical composition have been synthesized via Ar/O2 radio-frequency thermal plasma oxidation of mist precursor solutions with various Nb5+ concentrations (Nb/(Ti + Nb) = 0–25.0 at.%). The solubility as high as ∼25.0 at.% has not been achieved before by wet-chemical techniques. The preferable anatase formation was attained in the plasma-synthesized powders and was enhanced by the niobium doping. All the powders were heated at high temperatures (600–800 °C) to investigate their phase transformation, band gap variation, inter-particulate binding behavior, and photocatalytic stability. The transformation from anatase to rutile was effectively inhibited by increasing the Nb5+ content. The Nb5+ doping prevented the band gap of TiO2 from narrowing after the heating. At high temperatures, Nb5+ doping could not only preserve particle size but also prevent inter-particulate binding. High concentration (25.0 at.%) Nb5+ doping retained the photocatalytic performance almost invariably irrespective of being thermally treated.