Silicon nanocrystals (SiNCs) are nanometer-sized semiconducting materials. Their small size endows them with unique photophysical properties. Efficient photoluminescence (PL) from silicon nanocrystal (SiNC) composites has important implications for emerging solar-energy collection technologies, yet a detailed understanding of PL relaxation in non-colloidal SiNCs is still materializing. In this dissertation, we examine the photophysical properties of silicon nanocrystal/off-stoichiometry thiol-ene composites (SiNCs/OSTE hybrids). The dissertation begins with an introduction to the photophysical properties of SiNCs, their photophysical properties, how SiNC/polymer composites are made, the various SiNC preparation techniques, and the most likely application areas for these nanocrystals. A description of experimental methods such as PL spectroscopy and transmission electron microscopy (TEM) follows, and SiNC/OSTE polymer preparation methods are then explained in detail. In the first study, TEM and photophysical characterization were performed on selected polydisperse SiNCs samples. These samples were synthesized in a nonthermal plasma reactor, using Si6H12 as precursor, and functionalized with R (where R is 1-dodecene). These SiNCs were dispersed in mesitylene:1-dodecene (5:1) as a colloid. Optical absorption, quantum efficiency, and PL lifetime of SiNCs were then investigated, as well as the relationship between quantum yield, lifetime, and PL peak. In the second study, we selected samples for size separation via the density gradient ultracentrifugation method (DGU). We successfully applied this technique to separate silicon nanocrystals with sizes from 2 nm to 4 nm from the ensemble samples using an engineered density medium layer stack, and photophysical characterization was performed on the DGU size–separated SiNCs. Lastly, we explored details of PL relaxation in photo-polymerized off-stoichiometric polymer/nanocrystal hybrids. We found time- and air-stable emission from dilute composites with up to 70% QY, and we investigated PL relaxation in the parameter space of nanocrystal size and temperature. In light of previous work, our results reveal similarities between the impacts of crosslinking and cooling to cryogenic temperature, but of which are characterized by a relative reduction in the available of phonons.