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Through theoretical calculations, we show that integrating Pd with WO 3 nanomaterials can trigger the interfacial electron transfer from Pd to WO 3 , thus upshifting the d-band center (ε d ) of Pd to optimize toxic hexavalent chromium (Cr(VI)) reduction. The elevated ε d can derive stronger chemisorption capability toward crucial formic acid molecules, notably lowering the thermodynamic energy barrier and speeding up the kinetics process. In order to realize this concept, we synthesized unique Pd/WO 3 nanofibers by loading Pd nanoparticles onto electrospun WO 3 nanofibers through an in situ photodeposition technique. Extensive structural, morphological, and X-ray photoelectron spectrometer (XPS) characterizations confirm the successful formation of the above nanofibers. As anticipated, the as-designed Pd/WO 3 nanofibers exhibit enhanced catalytic performance in the Cr(VI) reduction with a high turnover frequency (TOF) value of 62.12 min -1 , surpassing a series of reported Pd-based catalysts. Such nanofibrous WO 3 -induced electronic modification of Pd with a high specific area leads to catalytic enhancement, providing a novel model for catalyst design., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)