This paper reviews the applications of super- and sub-critical carbon dioxide for the extraction of pharmaceuticals from various matrices. The matrices covered are divided into the following types: animal feed, formulations, biological and miscellaneous, with various sub-divisions as appropriate. The polar nature of most pharmaceuticals often precludes the use of carbon dioxide only, so it is common to find the addition of a more polar solvent, as modifier. As the majority of sample types covered are solid, little if any pre-treatment is required, with the exception of grinding, prior to insertion in the sample extraction cell. For liquid-type matrices, sample pre-treatment is the normal. Often this may involve adsorption on an inert support e.g. Celite or diatomaceous earth, or immobilisation on a functionalised silica surface, e.g. C18. The later may take the form of a solid phase extraction cartridge or disk. An attempt has also been made to sample from liquid matrices directly using a modified extraction cell. The variety of sample types, matrices and analyte polarity places stringent requirements on the use of pressurised carbon dioxide. Its potential for effective recovery is examined in this review.