Arrays of silicon nanowires (SiNWs) with characteristic transverse nanowire size of the order of 100 nm were fabricated by metal‐assisted chemical etching of monocrystalline silicon wafers followed by thermo‐diffusional doping with boron and studied by means of Raman spectroscopy considering the Fano effect related to the free charge carriers (holes) in SiNWs. The hole concentration of the order of 1020 cm−3 was shown to be achieved for SiNWs annealed at 950–1000°C and the peak intensity of Raman scattering of SiNWs dropped exponentially with the increasing free‐hole concentration. The obtained results can be used for the express diagnostics of the electrical properties of silicon nanostructures for applications in optoelectronics, sensorics, and thermoelectric devices.