Abstract Nowadays, the idea of Green Analytical Chemistry (GAC) is of high importance what impacts on the rapid growth in the sample preparation area with special emphasis on sample preparation simplification, miniaturization, and automation. Because the derivatization process is often an essential element of the analytical procedure, it should be important to focus on this issue from GAC perspective and conduct a series of experiments in order to develop the most favorable conditions. Application of microextraction techniques coupled with the derivatization perfectly meets the specified requirements. Other approaches to perform derivatization process in “green” way include the application of eco-friendly solvents/reagents, enhanced parameters such as microwaves or ultrasound and application of in-port, on-column/in-capillary derivatization modes. This review describes factors that allow making derivatization process more green, different modes and ways of derivatization procedures involving less toxic, hazardous reagents/solvents and more efficient forms of energy. Moreover, microextraction techniques that are often coupled to derivatization are described with examples.