Stratified optical filters with distinct spectral features and layered surface chemistry were prepared on silicon substrates with stepwise anodic porosification and thermal carbonization. The use of differing parameters for successive carbonization treatments enabled the production of hydrolytically stable porous silicon-based layered optical structures where the adsorption of water to the lower layer is inhibited. This enables selective shifting of reflectance bands by means of liquid infiltration. The merit of using thermal carbonization for creating layered functionality was demonstrated by comparing the hydrolytic stability resulting from this approach to other surface chemistries available for Si. The functionality of the stratified optical structures was demonstrated under water and ethanol infiltration, and changes in the adsorption properties after 9 months of storage were evaluated. The changes observed in the structure were explained using simulations based on the transfer matrix method and the Bruggeman effective medium approximation. Scanning electron microscopy was used for imaging the morphology of the porous structure. Finally, the adaptability of the method for preparing complex structures was demonstrated by stacking superimposed rugate structures with several reflective bands. © 2014 American Chemical Society.