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The photoluminescence (PL) response of porous Si has potential applications in a number of sensor and bioimaging techniques. However, many questions still remain regarding how to stabilize and enhance the PL signal, as well as how PL responds to environmental factors. Regenerative electroless etching (ReEtching) was used to produce photoluminescent porous Si directly from Si powder. As etched, the material was H-terminated. The intensity and peak wavelength were greatly affected by the rinsing protocol employed. The highest intensity and bluest PL were obtained when dilute HCl(aq) rinsing was followed by pentane wetting and vacuum oven drying. Roughly half of the hydrogen coverage was replaced with –RCOOH groups by thermal hydrosilylation. Hydrosilylated porous Si exhibited greater stability in aqueous solutions than H-terminated porous Si. Pickling of hydrosilylated porous Si in phosphate buffer was used to increase the PL intensity without significantly shifting the PL wavelength. PL intensity, wavelength and peak shape responded linearly with temperature change in a manner that was specific to the surface termination, which could facilitate the use of these parameters in a differential sensor scheme that exploits the inherent inhomogeneities of porous Si PL response.