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Natural products are increasingly becoming part of our daily lives through their use in industry, food, as therapeutic agents, etc. To evaluate their possible applications, it is essential to characterize them chemically to explore their potential. Different techniques may be used to characterize natural products, including microextraction techniques. These techniques have been gaining popularity due to the advantages associated with their low use of organic solvents and the small amount of sample used relative to more classical sample preparation techniques. Their application in the extraction of compounds from natural products is still scarce. This manuscript intends to review the most used solid-based miniaturized sample preparation techniques applied to determining compounds in natural products. The main applications of these methodologies will be discussed, with a particular focus on natural product analysis, as well as their advantages and disadvantages over traditionally used sample preparation techniques.