ABSTRACT δ-Bi2O3/Bi2SiO5 heterostructural photocatalysts with different contents of bismuth in samples (X-Bi-Si, where X = 10–60% Bi2O3) were prepared by the facile sol–gel method using bismuth nitrate and biogenic silica from rice husk biomass as precursors. FT-IR, scanning electron microscope, XRD, energy-dispersive X-ray fluorescence, and UV–Vis methods were systematically used to characterize the as-obtained materials. The photodegradation of methyl orange (MO) in neutral aqueous solutions (pH (6.8)) under UV irradiation was studied to evaluate their photocatalytic activities. The phase composition, morphology, and photocatalytic activity of the samples depended on the content of bismuth oxide in the samples. The maximum degree of MO degradation was 45% for 50-Bi-Si samples containing photoactive δ-Bi2O3 and Bi2SiO5 phases.