Dense ensembles of silicon nanowires were prepared by metal-catalyzed chemical vapor deposition on silicon substrates. Some of these ensembles were doped with phosphorous during growth. The nanowires were characterized using scanning electron microscopy, X-ray diffraction, and mass spectroscopy. Field emission of electrons from these structures was studied at room temperatures in ultra-high vacuum. The measurements were carried out using a parallel-plate diode cell. At high-applied fields, the current–voltage characteristics deviate from the Fowler–Nordheim law and exhibit a step-wise increase in the current with the increasing voltage at 300 K. Possible mechanisms of the observed quantized field emission are discussed.