The determination of trace analytes in complex natural matrices often requires extensive sample extraction and preparation prior to chromatographic analysis. Correct sample preparation can reduce analysis time, sources of error, enhance sensitivity and enable unequivocal identification, confirmation and quantification. This overview considers general aspects on sample preparation techniques for trace analysis in various matrices. The discussed extraction/enrichment techniques cover classical methods, such as Soxhlet and liquid-liquid extractions along with more recently developed techniques like pressurized liquid extraction, liquid phase microextraction (LPME), accelerated microwave extraction, and ultrasoundassisted extraction. This overview also deals with more selective methodologies, such as solid phase extraction (SPE), solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE). The adopted approach considers the equilibriums involved in each technique. The applicability of each technique in environmental, food, biological and pharmaceutical analyses is discussed, particularly for the determination of trace organic compounds by chromatographic methods.