Implementing green analytical methodologies has been one of the main objectives of the analytical chemistry community for the past two decades. Sample preparation and extraction procedures are two parts of analytical method development that can be best adapted to meet the principles of green analytical chemistry. The goal of transitioning to green analytical chemistry is to establish new methods that perform comparably—or superiorly—to traditional methods. The use of assessment tools to provide an objective and concise evaluation of the analytical methods’ adherence to the principles of green analytical chemistry is critical to achieving this goal. In this review, we describe various sample preparation and extraction methods that can be used to increase the greenness of a given analytical method. We gave special emphasis to modern microextraction technologies and their important contributions to the development of new green analytical methods. Several manuscripts in which the greenness of a solid-phase microextraction (SPME) technique was compared to other sample preparation strategies using the Green Analytical Procedure Index (GAPI), a green assessment tool, were reviewed.