This study explores the effectiveness of silicon quantum dots (SiQDs)—specifically, amine-functionalized (NSiQDs) and amine-hydroxyl-functionalized (NOSiQDs)—in optimizing thin-film nanocomposite (TFN) membranes for pervaporation dehydration of various alcohols. The SiQDs were integrated into the membranes via an innovative interfacial polymerization technique, involving the dispersion of SiQDs in an aqueous amine solution followed by polymerization with trimesoyl chloride. This approach ensured uniform integration of SiQDs, significantly enhancing the nanostructure and surface characteristics of the membranes. Such modifications led to improved water transport capabilities, substantially boosting pervaporation efficiency. Exceptional performance was demonstrated by the TFN-NOSiQDs(400) membranes, which achieved a peak permeation flux of 4195.8 g·m−2·h−1 and maintained over 99 wt% water concentration in the permeate when tested with a 70 wt% isopropanol/water solution at 25°C. Comprehensive long-term stability assessments confirmed the robustness and consistent functionality of the membranes, highlighting their suitability for industrial applications that demand reliable and efficient alcohol separation processes.