We describe the fabrication of a turn-off photoluminescent sensor for hydrogen fluoride (HF) vapour, based on silver-decorated porous silicon. Photoluminescence (PL) was achieved by thermal oxidation of the porous silicon layer. Silver was then deposited onto the porous layer using electroless deposition of silver nanoparticles (Ag NPs). HF sensing was based on the decrease of PL, which was itself linked to the etching of the oxide shell formed in the porous matrix. This HF-induced decrease in PL intensity was enhanced with the silver-containing nanostructures. Successful detection of HF vapour in highly humid conditions is demonstrated, with a lower limit of detection of 45 ppm.