Solid-phase microextraction (SPME) is a sample preparation technique which utilizes small amounts of an extraction phase for the extraction of target analytes from investigated sample matrices. Its simplicity of use, relatively short sample processing time, and fiber reusability have made SPME an attractive choice for many analytical applications. SPME has been widely applied to the sampling and analysis of environmental, food, aromatic, metallic, forensic, and pharmaceutical samples. Solid phase microextraction is used in horticultural crops, for example, to determine water and soil contaminants (pesticides, alcohols, phenols, amines, herbicides, etc.). SPME is also used in the food industry to separate biologically active substances in food products for various purposes, for example, disease prevention, determining the smell of food products, and analyzing tastes. SPME has been applied to forensic analysis to determine the alcohol concentration in blood and that of sugar in urine. This method has also been widely used in pharmaceutical analysis. It is a solvent-free sample preparation technique that integrates sampling, isolation, and concentration. This review focuses on recent work on the use of SPME techniques in the analysis of food and horticultural crops.