One type of nonlinear optical crystal Na3VO2B6O11 (NVB) with noncentrosymmetry was synthesized and shows extraordinary UV-visible light driven photocatalytic activity in the dechlorination of 2,4-DCP under UV-vis (lambda > 320 nm) light irradiation. The obtained dechlorination efficiency is 90 times higher than that of the commercial P25 TiO2 catalyst under the same conditions. The noncentrosymmetric structure of NVB gives rise to an intrinsic large polarization effect as evidenced by Kelvin probe force microscopy, and the polarization promotes separation of photogenerated electron-hole pairs, leading to efficient cleavage of chlorophenols into phenol series fragments and dissociative Cl- anions. A possible reaction pathway for 2,4-DCP dechlorination by NVB upon UV-vis light irradiation is proposed. Hydrodechlorination was found to be the major reaction pathway for 2,4-DCP dechlorination which could react with hydroxyl radicals to produce 1,4-benzoquinone and ocatechol. This work further advances the understanding of nonlinear optical materials, which opens up a new route to the design and synthesis of highly efficient photocatalysts by using nonlinear optical materials.