Luminescent silicon nanocrystals (ncSi) are showing great promise as photoluminescent tags for biological fluorescence imaging, with size-dependent emission that can be tuned into the near-infrared biological window and reported lack of toxicity. Here, colloidally stable ncSi with NIR photoluminescence are synthesized from (HSiO(1.5) )(n) sol-gel glasses and are used in biological fluorescence imaging. Modifications to the thermal processing conditions of (HSiO(1.5) )(n) sol-gel glasses, the development of new ncSi oxide liberation chemistry, and an appropriate alkyl surface passivation scheme lead to the formation of colloidally stable ncSi with photoluminescence centered at 955 nm. Water solubility and biocompatibility are achieved through encapsulation of the hydrophobic alkyl-capped ncSi within PEG-terminated solid lipid nanoparticles. Their applicability to biological imaging is demonstrated with the in-vitro fluorescence labelling of human breast tumor cells.