Eco-friendly epoxides produced from epoxidized vegetable oil have extensive utilization across various industrial applications. The epoxidation process relies heavily on the unsaturated content of vegetable oils as vital renewable feedstocks. The epoxide yield and quality are substantially influenced by the presence of carbon–carbon double bonds (C = C). The extractions of vegetable oil are mostly studied for obtaining high oil yield, and less attention was given to the unsaturation content of the fatty acids. This preliminary study investigates the most effective extraction strategies for preserving the unsaturation content of vegetable oils, thereby guaranteeing their efficacy in subsequent epoxidation reactions. The investigation concentrates on critical factors, including solvent selection, extraction conditions, and the utilization of assisted extraction methods, such as ultrasound and microwave techniques, to reduce the oxidative degradation of unsaturated bonds. In order to prevent excessive exposure to thermal or oxidative stress, operating parameters such as temperature and oxygen exclusion were optimized, and a variety of solvents were assessed for their polarity, selectivity, and compatibility with thermolabile compounds. The results underscore the significance of moderate, efficient extraction protocols in preserving the structural integrity of unsaturated fatty acids, thereby enhancing the feedstock potential of vegetable oils for sustainable chemical synthesis. This research establishes the groundwork for extraction processes that are more environmentally friendly and durable, specifically designed for epoxidation applications.