Well-dispersed Ag₃VO₄ nanoparticles @polyacrylonitrile (PAN) nanofibers were synthesized by an easily controlled, template-free method as a photo-catalyst for the degradation of methylene blue. Their structural, optical, and photocatalytic properties have been studied by X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy equipped with rapid energy dispersive analysis of X-ray, photoluminescence, and ultraviolet–visible spectroscopy. The characterization procedures revealed that the obtained material is PAN nanofibers decorated by Ag₃VO₄ nanoparticles. Photocatalytic degradation of methylene blue investigated in an aqueous solution under irradiation showed 99% degradation of the dye within 75 min. Finally, the antibacterial performance of Ag₃VO₄ nanoparticles @PAN composite nanofibers was experimentally verified by the destruction of Escherichia coli. These results suggest that the developed inexpensive and functional nanomaterials can serve as a non-precious catalyst for environmental applications.