Several hundred million volts per centimetre of electric-field strength are required to field-ionize gas species. Such fields are produced on sharp metallic tips under a bias of a few kilovolts. Here, we show that field ionization is possible at dramatically lower fields on semiconductor nanomaterials containing surface states, particularly with metal-catalysed whiskers grown on silicon nanowires. The low-voltage field-ionization phenomena observed here cannot be explained solely on the basis of the large field-amplification effect of suspended gold nanoparticles present on the whisker tips. We postulate that field penetration causes upward band-bending at the surface of exposed silicon containing surface states in the vicinity of the catalyst. Band-bending enables the valence electron to tunnel into the surface states at reduced fields. This work provides a basis for development of low-voltage ionization sensors. Although demonstrated on silicon, low-voltage field ionization can be detected on any sharp semiconductor tip containing proper surface states.