Phenolic compounds constitute a major class of plant secondary metabolites that are widely distributed in the plant kingdom and show a large structural diversity. These compounds occur as aglycones or glycosides, as monomers or constituting highly polymerized structures, or as free or matrix-bound compounds. Furthermore, they are not uniformly distributed in the plant and their stability varies significantly. This greatly complicates their extraction and isolation processes, which means that a single standardized procedure cannot be recommended for all phenolics and/or plant materials; procedures have to be optimized depending on the nature of the sample and the target analytes, and also on the object of the study. In this chapter, the main techniques for sample preparation, and extraction and isolation of phenolic compounds have been reviewed-from classical solvent extraction procedures to more modern approaches, such as the use of molecularly imprinted polymers or counter-current chromatography.