Surface stability is achieved and demonstrated by porous silicon (PS) fabricated using a wavelength-dependent photo-electrochemical (PEC) anodization technique. During anodization, the photon flux for all wavelengths was kept constant while only the effect of light wavelength on the surface morphology of PS was investigated. PS optical sensors were realized, characterized and tested using a photoluminescence (PL) quenching technique. An aliphatic chain of alcohols (methanol to n-octanol) was detected in the range of 10200ppm. Long term surface stability was observed from samples prepared under red (750620nm) and green illumination (570495 nm), where the PL quenching cycles evoke the possibility of using PS for stable sensor device applications. This study provides a route for preparing highly sensitive organic vapour sensors with a precise selection of the fabrication parameters and demonstrating their prolonged performance. © 2012 IOP Publishing Ltd.