Bi2WO6:Ho3+, Yb3+/g-C3N4 (BHY/CN) photocatalysts are successfully loaded on polyacrylonitrile (PAN) nanofibers by electrospinning technology, which combines an upconversion effect and heterojunctions to achieve dual-functional characteristics. Polymer-modified photocatalytic materials offer a large specific surface area of 24.1 m2/g and a pore volume of 0.1 cm3/g, promoting the utility of solar energy. The introduction of rare earth ions and g-C3N4 optimizes the structural band gap, which broadens the light absorption range and promotes electron transfer. Moreover, the heterojunction between Bi2WO6 and g-C3N4 has suppressed the complexation of photoinduced carriers, further improving catalytic performance. The optimized photocatalysts have higher photocatalytic activity with degrading 92.6% tetracycline-hydrochloride (120 min) under simulated sunlight irradiation. The optical thermometry has also been achieved based on the fluorescence intensity ratio technique, where the maximum absolute and relative sensitivity values of BHY/CN-1:6@PAN are 3.322% K-1 and 0.842% K-1, respectively. This dual-functional nanofibers with excellent mechanical properties provide noncontact temperature feedback and efficient catalytic performance for better wastewater treatment and ecological restoration in extreme harsh environments.