Silicon wires arrays have been produced by metal-assisted wet chemical etching with the use of crystalline silicon substrates. The arrays and individual nanowires have been studied by scanning and transmission electron microscopy. The electronic structure and phase composition of the surface and near-surface layers of the arrays have been studied by ultrasoft X-ray emission spectroscopy. It is shown that the morphologically more developed sample formed on a substrate with low resistivity is considerably more strongly subject to oxidation with noticeable formation of phases of intermediate silicon oxides. The array of nanowires formed on a substrate with high resistivity also undergoes natural oxidation, but does so to a substantially lesser extent and, with increasing depth of analysis, mostly contains the phase of crystalline silicon constituting the bulk of the nanowires being formed.