How to efficiently utilize visible light and highly separate photo-induced charges is now a hot topic in the field of photocatalysis. Herein, various amounts (1-5%, wt%) of Ag nanoparticles were selectively deposited on the surface of the polar material Na3VO2B6O11 (NVB) via the method of photoreduction. Due to the presence of external screening effect, the Ag nanoparticles were selectively deposited on the positive domains of NVB materials. Through DFT, the (110) facet with excessive electrons accumulated has a high reduction ability to deposit the Ag nanoparticles on the edge of NVB crystals. It was also found that the surface plasmon resonances effect of Ag nanoparticles led to the absorption spectrum of NVB broadened to the visible range around 400-800 nm. Under visible light irradiation, the photodegradation efficiency of NVB was significantly enhanced with the 4% Ag deposition, which reached 96% for 2-Chlorophenol (2-CP) degradation in 100 min. It indicates that the screening effect of NVB combination with the surface plasmon resonances effect from Ag nanoparticles can provide a synergistic effect on the enhanced photocatalytic activity during the 2-CP degradation.