The current clinical and forensic toxicological analysis of body fluids requires a modern approach to sample preparation characterized by high selectivity and enrichment capability, suitability for micro-samples, simplicity and speed, and the possibility of automation and miniaturization, as well as the use of small amounts of reagents, especially toxic solvents. Most of the abovementioned features may be realized using so-called microextraction techniques which cover liquid-phase techniques (e.g., single-drop microextraction, SDME; dispersive liquid–liquid microextraction, DLLME; hollow-fiber liquid-phase microextraction, HF-LPME) and solid-phase extraction techniques (solid-phase microextraction, SPME; microextraction in packed syringes, MEPS; disposable pipette tip extraction, DPX; stir bar sorption extraction, SBSE). Some other extraction methodologies like dispersive solid-phase extraction (d-SPE) or magnetic solid-phase extraction (MSPE) can also be easily miniaturized. This review briefly describes and characterizes the abovementioned extraction methods, and then presents their current applications to the preparation of body fluids analyzed for bioactive compounds in combination with appropriate analytical methods, mainly chromatographic and related techniques. The perspectives of the analytical area we are interested in are also indicated.