Silicon nanowires (SiNWs) were grown on an Au-coated Si(111) substrate at various gas pressures by very high frequency plasma enhanced chemical vapor deposition via the vapor–liquid–solid mechanism. The synthesized SiNWs were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy and photoluminescence (PL). The SiNWs were sharp needle-shaped and possessed highly crystalline core and oxide amorphous shell. As the gas pressure increases from 70 mtorr to 85 mtorr, the average diameter of the SiNWs decreases from 250 nm to 70 nm. Furthermore, the density of the nanowires increases with the gas pressure. The PL spectra revealed a peak at about 400 nm and a broadband emission at about 700 nm.