The bifunction of strong proton acidity and oxidation renders polyoxometalates (POMs) with great potential in catalysis. Utilizing their excellent catalytic activity to tackle antibiotic residues in water is meaningful but challenging. In this work, the self-induced synthesis of Ag₄V₂O₇ POM with a 3D nanorod-bundle structure was achieved by the local aggregation effect of the protons of sodium dodecyl sulfonate (SDS) under neutral conditions rather than an alkaline environment. The discovery of the bifunctionality of anionic surfactants provided a more convenient approach to synthesize materials for industry. The experimental results demonstrated that the degradation rate and reaction rate of Ag₄V₂O₇ POM to Rhodamine B dye were 4.64 and 30.00 times higher than a pure AgVO₃ catalyst, respectively. An increase in the A/V ratio of silver vanadium oxide (SVO) resulted in a negative shift of the valence band, accompanied by a decrease in the bandgap. Meanwhile, efficient separation and transmission of photogenerated carriers and increased surface hydroxyl density also intensified the photocatalytic activity of Ag₄V₂O₇ POM. In particular, Ag₄V₂O₇ POM was applied to antibiotic degradation creatively, resulting in an emerging class of catalysts for the degradation of antibiotics.