In this work, novel Bi14W2O27/Bi2WO6 nanocomposite was prepared by a modified Pechini sol-gel approach. The effect of the gelling agent, chelating agent and mole ratio of chelating agent to total metals was controlled to produce ultrafine Bi14W2O27/Bi2WO6 nanoparticles. The as-prepared Bi14W2O27/Bi2WO6 nanocomposite was characterized by XRD, FESEM, FT-IR, EDS and UV–Vis analysis. The Bi14W2O27/Bi2WO6 nanostructures exhibited excellent photocatalytic desulfurization of thiophene (~90%) after 120 min of simulated sunlight irradiation. The high-efficiency photocatalytic desulfurization of the as-prepared Bi14W2O27/Bi2WO6 can be attributed to the improved visible-light absorption, ultrafine nanoparticles, and high separation and low recombination rates of charge carriers. In addition, a reliable photocatalytic desulfurization mechanism was explained using radical trapping experiment, which indicated that the photogenerated •O2− and •OH species had a significant contribution in the photocatalytic desulfurization reactions of Bi14W2O27/Bi2WO6 nanocomposite. The excellent photocatalytic desulfurization efficiency, good recyclability, solar-driven, and simple synthesis of Bi14W2O27/Bi2WO6 nanocomposite are promising for photocatalytic applications. Manuscript profile