Investigations of nanoscale silicon powders obtained by plasma chemical synthesis in various process parameters were carried out by transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared (IR) spectroscopy. It was demonstrated that the powders consist of spherical particles with an average diameter from 20 to 30 nm. Each particle includes a single-crystal silicon core and amorphous shell whose chemical composition is defined by bonds of silicon with oxygen and hydrogen. The measurements of photoluminescence (FL) show the presence of dim near-infrared FL in the specimen powders, and more intensive emission around 420 nm in the suspension of the powder in ethanol. The character of this emission has not been determined yet.