Polysilane black powders were synthesized by sonochemical methods from silicon tetrachloride with sodium metal with 37.0% yield. Those black powder materials were found to have fibrous or irregular shapes with round surface. It was found that thermal behaviors of those polysilane black powders were similar to that of hydropolysilanes which was reported earlier. After thermal treatment, black polysilicon was obtained with 57.1% residue yield, and those fibrous or irregular shapes with round surface were intact but lots of small cavities were formed indicating porous structure, and found to be an amorphous state from XRD analysis.