Solid-phase microextraction (SPME) is a relatively new sampling technique wherein sample extraction and pre-concentration could be achieved in a single step. The handling of an SPME device is simple, and the analysis of volatiles could be easy. However, the process becomes complex while analyzing sample matrices of heterogeneous nature. The complexity also increases depending upon the nature of compounds to be extracted. Careful selection and optimization of extraction parameters like fiber coating selection, extraction time, agitation, addition of salt, and extraction temperature have to be undertaken to improve the sensitivity and the reproducibility of this method. This paper reviews the principles associated with SPME technique from a general application viewpoint. Also, a comprehensive review of prior research related to characterization of food quality has been reported. SPME-related solutions for environmental applications have also been analyzed to be applied for new food-related applications.