CMC/BiOCl 3D hierarchical nanostructures with exposed {001} facets were successfully synthesized under the control of carboxymethyl cellulose (CMC). The physicochemical properties of as‐synthesized samples were characterized by X‐ray powder diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV–vis diffused reflectance spectra (DRS), Fourier transformed infrared (FT‐IR), Brunauer‐Emmett‐Teller (BET) measurements, and electron spin resonance (ESR). The results demonstrate that CMC makes great effects upon the morphology, structure and properties. BOC‐1 synthesized with CMC amount of 0.1 g exhibits highest visible photocatalytic activity on the degradation of Rhodamine B (RhB) for its 3D hierarchical nanostructures, thinnest nanosheets about 8.6 nm, appropriate band gap about 2.82 eV. The reaction rate of BOC‐1 is 4.5 times higher than that of pure BiOCl synthesized without CMC. Furthermore, the radicals and holes trapping experiments and electron spin resonance spectroscopy confirm ⋅O2− is the main active species, and a possible mechanism of CMC/BiOCl enhanced the photocatalytic activity was proposed.