Novel B doped BiOCl nanocrystals (B-BiOCl) with exposed (001) facets were fabricated via a facile solvothermal route. The characterization methods of XRD, BET, SEM, TEM, UV–vis DRS, PL, EIS, ESR and photocurrent measurement were performed to investigate the physicochemical properties of the B-BiOCl samples. The results indicated that doping B into BiOCl could regulate and control the growth of (001) crystal facet, increase the specific surface areas and enhance the efficiency of charge separation. Hence, the optimal B1.0-BiOCl (atomic ratio of Bi:O:Cl: B is around 27.41: 28.27:25.43:3.55) exhibited significant promoting effect for the degradation of phenol, bisphenol A and rhodamine B than that of pure of BiOCl. The results of radical capturing and ESR analysis confirmed that the O2− radicals played a fatal role in the degradation of organic pollutants. This work could be expected to offer a new insight into design and synthesis of highly efficient photocatalyst with specific exposed facets by doping non-metallic elements. We designed a novel B-doped BiOCl photocatalyst with exposed (001) facets. This B-doped BiOCl displays significant performance in the degradation of organic pollutants. Display omitted •Novel B-BiOCl (001) photocatalyst was reported for the first time.•B doping improved the separation efficiency of photogenerated carriers.•B doping enhanced the photocatalytic degradation performance of OPs.•O2− played a fatal role in the degradation of OPs over B-BiOCl photocatalyst.