We have developed a one-step, hydrofluoric acid-free hydrothermal etching method that not only produces bismuth nano/micrometer-sized spheres but also prepares porous silicon with vertical holes. By controlling the heating temperature and time, nanoscale vertical-channeled porous silicon can be received. Our result indicated that the Bi clusters were formed first on the wafer surface. Then the etching of the Bi to the wafer creates the holes. Later, the Bi spheres went into the holes and expedited the etching process. A formation mechanism and chemical process have been proposed on the basis of experimental data. This simple chemistry approach may be of great scientific and technological importance for preparing porous silicon wafer.