A series of crystals Bi-III-VIA-VIIA, including the platelike crystals BiOCl, polygonal tubular crystals BiSCI, bundle-rodlike crystals Bi19S27Br3, and BiSI, have been grown with use of mild solution routes in an ethanol system. The products are characterized by means of X-ray powder diffraction (XRD), electron diffraction (ED), scanning electronic microscopy (SEM), and Raman spectrum techniques. A possible mechanism of the reaction and of the growth of the crystals is proposed.