Two isostructural d(10) configuration non-centrosymmetric materials: K3ZnB5O10 (KZBO) and K3CdB5O10 (KCBO) can act as efficient and reusable catalysts in the dehalogenation of halophenols. More than 90% of the 2, 4-DXP were degraded within 10 min with the dehalogenation efficiency 2, 4-DBP > 2, 4-DCP > 2, 4-DFP, the dehalogenation efficiency is almost 10 times higher than that of commercial P25 TiO2 catalyst in the present reaction conditions. The internal electric field due to the distorted [MO4] tetrahedral and [BO3] units promote the charge separation in the initial process of photoexcitation and d(10) configuration of Zn and Cd with large dispersion is useful for photoexcited electron transfers without recombination, thus enhance the photocatalytic activity. The dehalogenation pathways with KCBO outlined both oxidative and reductive dehalogenation. Our work is expected to offer new insight into photocatalytic theory for better understandings to photocatalytic reactions and rational design and synthesis of photocatalysts with high activity.(C)2017 Published by Elsevier B.V.