Although solar-driven hydrogen production and recalcitrant pollutant degradation are appealing technologies, the photocatalytic efficiency for most reactions is limited by insufficient visible-light harvesting ability and restricted charge transfer pathways. To tackle these obstacles, we designed novel photocatalyst Fe2O3/CuxO/TiO2(B) nanofibers (namely, CFTNF-y) viaan in situphotodeposition strategy. The effects of the CuxO nanoparticle concentration on TiO2(B) nanofibers (CTNF-x) were investigated, and the optimized catalyst was compared to other synthesized catalysts viaa chemical reduction strategy (CTNF-x(NS)). The formation of Fe2O3/CuxO nanoparticles on the TiO2(B) nanofiber (TNF) surface in CFTNF-ynanocomposites was confirmed by HAADF-STEM, elemental mapping, XRF, XPS, XANES and EXAFS results. The CFTNF-ynanocomposites demonstrated a significantly enhanced photocatalytic hydrogen production activity of 65.82 μmol g−1h−1under UV-visible light irradiation, which was 12-fold higher than that of pristine TNF. Moreover, the CFTNF-ynanocomposites exhibited a photocatalytic trimethoprim (TMP, a model antibiotic contaminant) removal rate of 0.1 mM g−1min−1. These excellent photocatalytic performances can be attributed to the uniform distribution of size-controlled Fe2O3/CuxO nanoparticles on the TNF surface, improved light-harvesting ability in the visible region and a remarkable charge carrier separation/transfer rate realized viaa dual-Z-scheme heterojunction mediated by an interfacial electric field. This assertion is supported by morphology analysis, ERDT/CBB by RDB-PAS, radical trapping experiments, and photoelectrochemical studies. Moreover, a plausible TMP photodegradation pathway over CFTNF-ynanocomposites is proposed based on LC-MS/MS analysis. The present work highlights a novel approach for the development of a dual-Z-scheme photocatalyst with interfacial charge transfer for achieving efficient photocatalytic performance.