An investigation on unusual interface properties of unprecedented ternary composites, formed by the inclusion of assorted proportions of B2O3 into TiO2/SiO2 structure, is conducted herein. The influences of B2O3 content and calcination temperature were evaluated. The precursor TiO2/SiO2 material was synthesized via a simple sol-gel procedure that was followed by B2O3 inclusion via maceration and calcination. The materials were fully characterized and their photocatalytic performance to degrade the Indigo Carmine dye investigated. The material prepared with a B/Ti molar ratio of 1 and at calcination temperature of 350 °C (B1-350) showed the best performance, with a superior photocatalytic activity than that of commercial TiO2. The presence of B2O3-TiO2-SiO2 interfaces in the structure of such material was of critical importance in producing a material with these attractive features. Finally, high resolution mass spectrometry monitoring allowed for the characterization of the main degradation products formed under these conditions.