In present time, the selective extraction of molecules assisted by pulsed electric fields (PEF) has gained growing interest. The PEF can serve as an effective tool for improvement of traditional extraction processes in biotechnological and food industries. The PEF-assisted extraction can be applied in two different modes: by diffusion in solvent (solvent extraction) and by pressing (solid-liquid expression). The PEF-assisted extraction methods are suitable for the selective recovery and extraction of sugar, inulin, starch, proteins, polysaccharides, polyphenols, pigments, flavor compounds, phytochemicals, and other of high-value components. The PEF can be applied for treatment of different fruits and vegetables (apple, carrot, table beet, etc.), leaves (tea, spinach), herbs, mushrooms, and suspensions of cells (yeasts, microalgae, etc.). The PEF-assisted techniques have low operating costs and can be applied to the thermally sensitive products in “cold” mode without deterioration of color, flavor, vitamins, and other important nutrients of foods. “Cold” refers to the fact that only mild heat is added during extraction procedure. In this chapter the main extraction procedures assisted by PEF are defined. The different examples of PEF-assisted solvent extraction and expression of useful components from different food and biomaterials are collected. The emphasis is placed on the selectivity of extraction. Following the handbook format, the chapter is concise and covers various common features of PEF processing, review on recent efforts in the field, as well as several aspects of our own research.