Bulk quantities of defect-free silicon (Si) nanowires with nearly uniform diameters ranging from 40 to 50 angstroms were grown to a length of several micrometers with a supercritical fluid solution-phase approach. Alkanethiol-coated gold nanocrystals (25 angstroms in diameter) were used as uniform seeds to direct one-dimensional Si crystallization in a solvent heated and pressurized above its critical point. The orientation of the Si nanowires produced with this method could be controlled with reaction pressure. Visible photoluminescence due to quantum confinement effects was observed, as were discrete optical transitions in the ultraviolet-visible absorbance spectra.