Silicon (Si) nanostructures were prepared in the downstream of radiofrequency SF 6 /O 2 mixture plasma generated in 13.56 MHz hollow cathode discharge system. Depending on the oxygen percentage in the mixture, the obtained Si nanostructures were characterized for their different properties: etching rate, morphology, optical reflectance, photoluminescence, spectral response and humidity sensing. It is found that the etching rate exhibits a maximum value when the O 2 ratio reaches 5%. An interesting defect-induced "violet" luminescence is reported from the Si nanostructures, whose intensity depends on their density. The obtained Si nanostructures have shown to induce a spectral response (SR) enhancement, in comparison with a smooth Si substrate, of about 100 times at 1100 nm wavelength. A very short response time (1 sec) to the humidity was measured for 5% O 2 in the SF 6 /O 2 plasma mixture, which was found to be well-correlated with the porosity of the Si nanostructures.