This chapter will describe some of the main separation techniques, considered environmentally correct, with special emphasis on sample preparation. To illustrate aspects of green analytical chemistry, techniques for sample preparation and hyphenation capable of miniaturization will be presented, which reduce, replace or eliminate the use of hazardous organic solvents focusing on organic analytes in complex matrices, mainly based on supercritical fluid extraction, membranes, solid phase extraction, matrix solid phase dispersion as well as sorptive extraction techniques, including some examples of their uses.