Given the complexity of injurious ingredients in practical wastewater, development of effective and low-cost multifunctional materials to decontaminate wastewater is of great necessity. Herein, polyacrylonitrile (PAN)/AgBr/Ag fibrous membranes are rationally designed and fabricated using combined electrospinning and wet-chemical methods. The surface AgBr/Ag Schottky junction is simply generated on hydrophilic PAN fibers by epitaxial growth approach, which simultaneously reveals superior photodegradation performance towards a variety of mimetic organic pollutions and excellent antibacterial activity due to their electron synergetic effect. Moreover, the stable porous structure of PAN/AgBr/Ag membranes and its good mechanic strength also ensures its good filtration performance. Overall, the PAN/AgBr/Ag fibrous membrane reveals water purification ability towards the simulated wastewater. In addition, benefit from the low content of Ag in PAN/AgBr/Ag membrane and easily scale-up, the self-standing PAN/AgBr/Ag membrane reveals great potential to practical wastewater treatment.