Aflatoxins (AFs) are well-known mycotoxins and contaminants of various agricultural commodities globally that are linked to a wide range of adverse health and economic complications. Because of their incessant proliferation and deleterious consequences, it has become mandatory to routinely monitor the levels of these toxins in agricultural products before they go into the market. Essentially, effective analysis is an important component of AFs control, and extraction is a necessary step for their analysis, irrespective of the protocol adopted. Conventional methods for AF extraction are expensive, the processes involved are tedious and utilize large quantities of organic solvents that are environmentally unfriendly. This has necessitated the quest for alternatives that are 'green', cost-effective and easy to perform. In this regard, subcritical water extraction (SWE) is a viable alternative that has proven to be effective in the extraction of other bioactive compounds. This chapter presents a critical appraisal of the principles and dynamics of SWE, and its current applications as a viable tool in the extraction of AFs from various biological matrices. Although further research needs to be performed to enhance its applicability, the adoption of SWE in the extraction of AFs seems very promising and needs to be properly exploited.