Present work reports the enhancement in photocatalytic performance of Ag3PO4 nanoparticles through sulfate doping and anchoring on Polyacrylonitrile (PAN)-electrospun nanofibers (SO42--Ag(3)PO(4/)PAN-electrospun nanofibers) via electrospinning followed by ion-exchange reaction. Morphology, structure, chemical composition, and optical properties of the prepared sample were characterized using XRD, FESEM, FTIR, XPS, and DRS. The anchoring of SO42--Ag3PO4 nanoparticles on the surface of PAN-electrospun nanofibers was evidenced by the change in color of the PAN nanofibers mat from white to yellow after ion-exchange reaction. FESEM analysis revealed the existence of numerous SO42--Ag3PO4 nanoparticles on the surface of PAN nanofibers. Photocatalytic activity and stability of the prepared sample was tested for the degradation of Methylene blue (MB) and Rhodamine B (RhB) dyes under visible light irradiation for three continuous cycles. Experimental results showed enhanced photodegradation activity of SO42--Ag3PO4/PAN-electrospun nanofibers compared to that of sulfate undoped sample (Ag3PO4/PAN-electrospun nanofibers). Doping of SO42- into Ag3PO4 crystal lattice could increase the photogenerated electron-hole separation capability, and PAN nanofibers served as support for nanoparticles to prevent from agglomeration.