Porous silicon (PS) was characterized by 1H, 19F and 29Si solid-state nuclear magnetic resonance (NMR). On freshly prepared samples, hydrogen contents were between 3 × 1014 and 3 × 1015 per cm2 of PS surface area, while fluorine concentrations were below the detection limit. Cross-polarization (CP) was used to selectively observe the 29Si near the hydrogen passivation. The features of the 29Si NMR spectra are assigned as (O)2(Si)Si-H (-50 ppm), (O)3Si-H (-84 ppm), (Si)3Si-H (-91 ppm), (Si)2Si-H2 (-102 ppm) and (O)4Si (-109 ppm). Changes resulting from low temperature annealing in air and an HF soak were observed by both NMR and infrared spectroscopy. The 29Si NMR line widths for PS fall between those for crystalline silicon and those for amorphous hydrogenated silicon films (a-Si:H), suggesting disorder near the PS surface is intermediate between these extremes. However, comparison of the isotropie chemical shift values shows that the bonding in the disordered regions of PS differs from that found in a-Si:H. In addition, the sharp 29Si NMR resonance observed in the bulk single crystal starting material can not be resolved in the spectra of PS. Thus, well-ordered silicon nanocrystallites in the PS are either several bond-lengths removed from hydrogen or comprise only a small fraction of the PS layer.