Tungsten trioxide (WO3) based nanofibers have many advantages as photocatalysts due to its band gap which fits with readily accessible light sources. We successfully fabricated novel palladium oxide (PdO) particles decorated WO3 nanofibers by electrospinning combined with chemical deposition processes, leading to improved photocatalytic efficiency for organic dye degradation up to 86.4%. Morphologies, elemental compositions and structural analyses confirmed the successful uniform decoration of PdO particles along WO3 nanofibers. Photodegradation of methylene blue as a model pollutant in water media was performed under UV and visible light in the presence of fabricated nanofibers as a photocatalyst. As a result, improved photocatalytic activity by PdO decoration was observed compared to commercially available WO3 NFs without PdO, attributed to its ability to hold excited electrons and increase surface area of NFs. This fibrous hybrid catalytic materials platform will open up a new and practical route and stimulate further research to improve photocatalytic performance.