Bismuth oxychloride (BiOCl) sub-microcrystals with tunable morphologies from nanoflakes to hollow microspheres (HMSs) have been synthesized by hydrolyzing a hierarchical precursor (BiCl3) in a solution of water and ethanol with the addition of poly(vinylpyrrolidone) (PVP) and citric acid. The obtained BiOCl possessed sub-microcrystals from single crystals to polycrystals. The formation of the nestlike and hollow structure was found to be induced by citric acid and PVP. The crystal growth and morphology control of BiOCl were explored. Interestingly, citric acid was utilized both as a crystal-growth-inducing agent and a structure-directing agent. The morphology and compositional characteristics of BiOCl were investigated by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Raman, and UV–vis spectra. The photocatalytic activities of BiOCl with different structures have also been investigated by the degradation of Rhodamine-B (RhB) dye under ultraviolet light irradia...