A series of La-doped BiOCl hierarchical, flower-like nano-/micro-structures (NMFs) with ginkgo-leaf-like "petals" were prepared by etching La-doped Bi2O3 films in HCl solution at room temperature. For the La-doped Bi2O3 films, they were fabricated through hot-dipping Bi2O3 thin films in La2O3 powder at 650 degrees C. Microstructure examination revealed that the ginkgo-leaf-like La-doped BiOCl petals have a multilayered structure consisting of several ultra-thin nanosheets with different radii due to the external-to-internal etching process. The investigation on their formation mechanism revealed that the La-doped BiOCl hierarchical NMFs grew anisotropically through Ostwald ripening mechanism. Besides, the photodegradation of rhodamine B under simulated sunlight irradiation revealed that the La-doped BiOCl hierarchical NMFs possessed higher performance than pure BiOCl sample. And the active species trapping tests indicated that the photogenerated holes were the main active radicals for the degradation of rhodamine B.