One of the many environmental challenges faced by Extraction field is the widespread use of organic solvents. With a solvent based extraction the solvent necessarily has to be separated from the final extract. A large number of these solvents are toxic that pose a risk to workers and community members and virtually all of them are classified as volatile organic compounds (VOCs) that contribute to smog. In this context, the development of solvent-free extraction processes is of great interest in order to modernize classical processes making them cleaner, safer and easier to perform. This chapter presents a picture of current knowledge on innovative solvent-free methods of natural products extraction. It provides the necessary theoretical background and some details about extraction using the most innovative, rapid and green techniques such as microwaves, instant controlled pressure drop (DIC) process and Pulsed Electric Field (PEF): the technique, the mechanism and some applications.