Three-dimensional flower-like Eu3+ and Sm3+-activated BiOCl globular microarchitectures were synthesized by the solvothermal method employing urea as a dispersing agent for the first time. The crystal structure, morphologies and luminescence properties of Eu3+ and Sm3+ doped BiOCl have been systematically investigated by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) and spectroscopy, respectively. The unit cell volumes show a nearly linear decrease by about 0.18 and 0.15% with increasing Eu3+ and Sm3+ concentration up to 9 mol%, respectively. All of the prepared samples show flower-like globular microarchitectures with an average diameter about 3-5 mu m with different Eu3+ and Sm3+ concentrations. Possible formation mechanism for the flower-like microarchitectures is proposed on the basis of time-dependent experiment. Both BiOCl:Eu3+ and BiOCl:Sm3+ samples show a strong red emission corresponding to the (D0 -> F4)-D-5-F-7 transition (700 nm) of Eu3+ and (4)G(5/2)-> H-6(7/2) transition (600 nm) of Sm3+, respectively. This work sheds some light on the design and preparation of red-emitting phosphors with novel microstructures. (C) 2015 Elsevier B.V. All rights reserved.