This study aims to develop structurally controlled TiO2-based materials that serve a dual purpose as high-performance photocatalysts and optical scattering agents for white light-emitting diodes (LEDs). Hollow spherical TiO2, TiO2/Ag, and TiO2/Au particles were synthesized via a one-step spray thermolysis process using aqueous titanium citrate and titanium oxalate precursors. The method enables precise control of morphology and crystalline phase composition, producing hollow microspheres with tunable anatase–rutile ratios (10–100%) and crystallite sizes ranging from 12 to 120 nm. Photocatalytic performance, evaluated through the ultraviolet (UV)driven oxidation of methylene blue, showed that as-prepared TiO2 exhibited comparable activity to Degussa P25, while metal doping accelerated the anatase-to-rutile transition with minimal plasmonic enhancement under UV light. For LED applications, incorporating hollow TiO2 particles into YAG:Ce phosphor films improved luminous intensity, reaching a peak of ∼71 lm at 1 wt.% TiO2, and enhanced color uniformity, achieving a D-CCT as low as ∼60 K at 5 wt.%. These results confirm that spray thermolysis provides a scalable route to tailor morphology and phase composition, enabling multifunctional TiO2 materials optimized for both environmental photocatalysis and high-quality LED lighting.