摘要：Bismuth‐based photocatalysts are a class of excellent visible‐light photocatalysts;however,their redox activity is relatively poor and the efficiency of photogenerated carrier separation is low,limiting their development and application in the field of *** address these issues,a series of polyoxometalate PW_(12)O_(40)^(3–)‐doped Bi_(2)O_(3–x)/Bi Schottky photocatalysts PW_(12)@Bi_(2)O_(3–x)/Bi‐n(PBOB‐n,where n is the amount of NaBH4,i.e.,6,12,18,24,and 48 mg)were prepared by a simple electrospinning/calcination/in‐situ NaBH4 reduction *** this composite photocatalyst,the doping of PW_(12) could effectively adjust the electronic structure of Bi_(2)O_(3–x) and improve its redox *** a shallow electron trap,PW_(12) promoted the separation of the photogenerated ***,desirable Schottky junction between the metal Bi nanoparticles and PW_(12)@Bi_(2)O_(3–x) further accelerated the separation of the photogenerated *** synergistic effect of the aforementioned factors endowed PBOB‐n with excellent photocatalytic *** the samples,PBOB‐18 exhibited superior photocatalytic *** visible‐light irradiation,93.7%(20 mg catalyst)of 20 ppm tetrabromobisphenol A(TBBPA,20 mL)was degraded in 60 *** activity was 4.4 times higher than that of Bi_(2)O_(3).PBOB‐18 also exhibited an ultrahigh photocatalytic performance for the removal of *** removal rate(600 ppb)reached 83.3%in 30 min,making it one of the most active Bi‐based ***,the photocatalytic mechanisms of PBOB‐18 for TBBPA and NO have been *** work provides a new direction and reference for the design of low‐cost,efficient,stable,and versatile photocatalysts.