H-terminated porous silicon (PSi) surfaces were chemically modified with terminal alkenes and aldehydes at high temperature to yield organic monolayers covalently attached to the surface through Si-C and Si-O-C bonds, respectively. Diffuse reflectance infrared Fouriertransform and X-ray photoelectron spectroscopies have been used to characterize the surfaces. Derivatized surfaces retain the PSi photoluminescence. Chemography was used to monitor the chemical changes of the PSi surface when exposed to 100% humidity in air. Organic monolayers linked through Si-C bonds are found to be highly resistant and have shown a better protection of the surface against corrosion compared to surfaces that are linked through Si-O-C bonds. The surface functionalized with ethyl undecylenate exhibits an even higher passivation of the surface through the presence of small amounts of oxide, which are induced by traces of water present in this chemical reagent, along with organic molecules attached to the surface.