Efficient and recyclable water treatment technology plays a vital role in practical application of Cr(Ⅵ)removal. Zr-based metal–organic framework (UiO-66-NH2) is widely used in wastewater treatmentdue to its water stability. Powdery UiO-66-NH2 has disadvantages of easy aggregation, reclamation difficultyand secondary pollution. In this work, UiO-66-NH2 was successfully loaded on electrospunpolyvinylidene fluoride (PVDF) fibers by in-situ growth to achieve efficient adsorption and photoreductionof Cr(Ⅵ). Grooved surface of PVDF fibers and truncated octahedron shape of UiO-66-NH2 ensuredthe loading uniformity and firmness. The loading rate and size of UiO-66-NH2 crystals increased withthe amount of trifluoroacetic acid (TFA) in the preparation process. Meantime, the introduction of TFAin synthesis was conducive to the separation efficiency of photogenerated carries. When the additionamount of TFA was 5 ml, UiO-PVDF-3 with loading rate of 44.8% exhibited best Cr(VI) adsorption andphotocatalysis performance. For the pure adsorption process, the adsorption capacity of UiO-PVDF-3 at90 min was 3.76 mg/cm2, and the corresponding removal rate was 95.8%. When visible light was applied,the Cr(VI) removal rate for UiO-PVDF-3 reached to about 95.0% at 45 min. Furthermore, regenerationexperiments showed UiO-PVDF-3 had excellent adsorption and photocatalysis reusability. Based on thismethod, synthesized UiO-66-NH2/PVDF hybrid membrane as a bifunctional material for adsorption andphotocatalysis realizes the reuse of UiO-66-NH2 crystals conveniently and avoids secondary pollutionduring Cr(VI) wastewater treatment.