The optical use of colloidal silicon nanocrystals (Si NCs) has gained increasing attention for its possible contributions to building a sustainable society that ideally uses resources and energy with high efficiency without causing damage to the environment or human health. Si wafers (E(g) ≈ 1.1 eV) dominate modern microelectronics as an impressive electronic material, but they exhibit relatively poor optical performance owing to an indirect bandgap structure. Interestingly, however, full control of the size distribution and surface chemistry of the NCs yields size-dependent light emission in a very wide range from near-ultraviolet through visible to near-infrared wavelengths. In addition to such unique luminescence properties, Si exhibits a high chemical affinity to covalent linkages with carbon, oxygen, and nitrogen, thereby producing almost unlimited variations in organic-Si NCs architectures hybridized at the molecular level. To achieve this goal, I note some parameters, including interfacial chemistry, that are emerging as important elements for increasing our understanding of the effect of quantum confinement in nanostructured Si and for realizing efficient fluorescence emission. This article covers new aspects of derivatives of Si NCs in applications that utilize their optical absorption and emission features.