The use of green extraction phases has gained much attention in different fields of study, including in sample preparation for the determination of organic compounds by chromatography techniques. Green extraction phases are considered as an alternative to conventional phases due to several advantages such as non-toxicity, biodegradability, low cost and ease of preparation. In addition, the use of greener extraction phases reinforces the environmentally-friendly features of microextraction techniques. Thus, this work presents a review about new materials that have been used in extraction phases applied to liquid and sorbent-based microextractions of organic compounds in different matrices.