Heavy-metal-free fluorophores such as silicon quantum dots (SiQDs) are required for next-generation light sources to address environmental concerns. However, few studies on SiQD devices are concerned with flexible devices, luminescence colors other than red, or stability data. Herein, the synthesis via three different methods of colloidal SiQDs exhibiting red/green/blue (RGB) photoluminescence (PL) is presented. The durability of each RGB SiQD embedded in a flexible polymer film (>4 × 4 cm 2 ) and exposed to solar light or hot water is evaluated. The nature of the terminating ligand on the SiQD surface significantly affects PL stability. In particular, SiQDs passivated with siloxane groups exhibiting blue PL retained 80% of their initial PL intensity after solarlight exposure for 8 days. These blue SiQDs embedded in a film retain 94% of their original PL quantum yield (PLQY) after 12 days at 80 °C in water. The types of ligand, coverage, and host material properties (light absorptivity, permeability, and hydrophobicity) are critical for enhancing the PLQY, radiative rate, and durability of SiQDs. These new insights are invaluable for designing heavy-metal-free light sources, accelerating their use, implementing them, and integrating them into curved substrates with soft textures and improved flexibility and stretchability, leading to foldable optoelectronics, e-skins, and wearable devices.