When porous silicon is transferred into a non-fluoride electrolyte and anodically oxidized, the onset of red electroluminescence during anodic oxidation appears correlated with a decrease in the OH IR absorption bands, indicating significant electrolyte removal from the ports. The electron states whose population is affected by carrier injection or light excitation have been investigated using in situ electromodulated or photomodulated IR spectroscopy. The modulated IR absorption of red-luminescent electro-oxidized porous silicon exhibits an extra absorption of localized carriers in the 1000-2500 cm(-1) region, suggesting that the red luminescence occurs through carriers trapped in localized states. The localization process may be efficiently affected by the dielectric constant of the medium surrounding the silicon nanocrystallites.