Bi(Er3+-Yb3+)VO4　fibers　prepared　by　the　iterative　electrospinning　process　have　excellent　crystal　filament　compatibility.　Compared　with　traditional　photocatalytic　materials,　fibers　in　our　work　are　admirable　in　some　aspects　including　large　specific　surface　area,　strong　three-dimensional　weaving　capacity,　high　solar　energy　utilization　rate,　high　reproducibility,　and　controllable　structure.　The　working　temperature　of　the　catalytic　degradation　process　is　monitored　and　fed　back　in　real　time　by　2H11/2　-4I15/2　and　4S3/2　-4I15/2　radiation　transitions　of　Er3+　with　excellent　sensitivity.　Photocatalytic　efficiency　is　greatly　improved　by　broadening　the　photoresponse　range　of　BiVO4　and　inhibiting　the　recombination　of　photo-generated　charges,　which　is　attributable　to　the　successful　incorporation　of　rare　earth　ions.　The　maximum　degradation　efficiency　of　methylene　blue　(MB)　is　98.7%　and　the　degradation　constant　K　is　as　high　as　0.116　min-1　under　simulated　sun-light　irradiation　and　it　also　has　the　same　degradation　trend　under　near-infrared　(NIR)　light　irradiation.　In　general,　highly　efficient　catalytic　fibers　with　sensitive　temperature　feedback　performance　provide　a　new　perspective　for　the　application　of　multifunctional　photocatalytic　materials　in　extremely　harsh　environments　to　address　pressing　energy　and　environmental　challenges.