Bi2WO6:　Er,　Yb　nanofibers　prepared　via　solvothermal-electrospinning　method　have　high-efficiency　photocatalysis　performance　and　superior　temperature　feedback.　Combining　crystal　integrity　and　polymer　processability,　polyacrylonitrile　composite　fibers　are　commendable　in　many　aspects,　such　as　large　specific　surface　area,　excellent　flexibility,　controllable　structure　and　high　solar　energy　utilization.　The　boost　in　photocatalysis　activity　can　be　attributable　to　non-radiative　energy　transfer　between　Er3+　ions　with　bismuth　tungstate　and　doping　effect　of　rare　earth　ions　in　Bi2WO6,　where　this　doping　enhances　separation　efficiency　of　electron-hole　pairs　and　promotes　generation　of　highly　oxidative　species.　The　electrospun　nanofibers　also　can　accurately　perform　contact-free　temperature　monitoring　and　real-time　thermal　feedback　on　the　degradation　system　through　H-2(11/2)　-＞　I-4(15/2)　and　S-4(3/2)　-＞　I-4(15/2)　radiation　transitions　of　Er3+　ions.　In　addition,　the　absolute　sensitivity　S-A　and　the　relative　sensitivity　S-R　are　as　high　as　0.868%　K-1　and　1.548%　K-1　at　313　K,　respectively,　which　indicates　nanofibers　have　good　thermal　sensitivity.　This　dual-function　nanofiber　provides　new　application　prospects　for　the　development　of　innovative　multifunctional　semiconductor　materials　to　cope　with　the　ecological　and　energy　crisis.