Laboratory extraction methods are essential for obtaining native starch in adequate quantity and quality for characterization, especially from underexplored raw materials. Aqueous extraction techniques and those with a reducing agent, such as active SO2, are used when raw materials have a high protein content and/or enzymatic browning enzymes, making starch separation difficult and promoting the formation of brownish starches, respectively. Some raw materials also contain carbohydrates and proteins that can undergo fermentation during maceration in water, so bisulfite inhibits microorganisms. This chapter covers the main methods, as well as precautions, standardization, and strategies to optimize the yield and purity of the extracted starch.