The role of surface species in the optical properties of silicon nanocrystals (SiNCs) is the subject of intense debate. Changes in photoluminescence (PL) energy following hydrosilylation of SiNCs with alkyl-terminated surfaces are most often ascribed to enhanced quantum confinement in the smaller cores of oxidized NCs or to oxygen-induced defect emission. We have investigated the PL properties of alkyl-functionalized SiNCs prepared using two related methods: thermal and photochemical hydrosilylation. Photochemically-functionalized SiNCs exhibit higher emission energies than the thermally-functionalized equivalent. While microsecond lifetime emission attributed to carrier recombination within the NC core was observed from all samples, much faster, size-independent nanosecond lifetime components were only observed in samples prepared using photochemical hydrosilylation that possessed substantial surface oxidation. In addition, photochemically modified SiNCs exhibit higher absolute photoluminescent quantum yields (AQY) consistent with radiative recombination processes occurring at the oxygen-based defects. Correlating spectrally- and time-resolved PL measurements and XPS-derived relative surface oxidation for NCs prepared using different photo-assisted hydrosilylation reaction times provides evidence the PL blue-shift as well as the short-lived PL emission observed for photochemically functionalized SiNCs are related to the relative concentration of oxygen surface defects.