In this Article, we report on the encapsulation of decyl-modified silicon nanoparticles (decyl-SiNPs) into similar to 80 nm lipid nanocapsules (LNCs). The decyl-SiNPs were produced by thermal hydrosilylation of hydride-terminated SiNPs (H-SiNPs) liberated from porous silicon. Various techniques, including Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), UV-vis absorption, dynamic light scattering (DLS), and photoluminescence (PL), were used to characterize their size, shape, colloidal, and optical properties. The results indicate that these nanocapsules feature controllable size, good dispersity, high loading rate of SiNPs, colloidal stability in various media, and bright PL. The PL of decyl-SiNPs loaded LNCs was stable upon heating to 80 degrees C, but was sensitive to basic solutions due to proton-gated emission of the SiNPs arranged at the LNCs interface between the oil phase and the hydrophilic polyethylene glycol moieties of the surfactant. These luminescent nanocapsules are therefore promising candidates as cellular probes for fluorescence imaging. In imaging of small-sized decyl-SiNPs could be greatly improved by preliminary negative staining of TEM grids with phosphotungstic acid.