This review introduces a new and innovative area in the frontiers of chemistry, biology and processing: green extraction with special emphasis on natural products processing. Green extraction is a part of the sustainable development and industrial strategy; its history, concept, principles, and fundamentals are described. We pay special attention to the strategies and the tools available to make biorefinery greener. This review presents the innovative research in this area in the past five years in terms of innovative techniques (microwave, ultrasound, instantaneous pressure drop, supercritical fluid extraction, pressing) applied to green extraction of natural products with special examples applied to biorefinery concept.