Mixtures of chemical compounds were analyzed to discriminate constituents of binary gas mixture using porous silicon. Time-resolved reflectivity measurements were used to analyze ethanol and acetone mixtures. The components of the binary mixtures were separated temporally in the porous silicon film. The porous silicon films played a dual role of separation column and detector. Results showed that pore size, length, and surface derivatization of the porous Si matrix could be adjusted to optimize specificity.