Due to their extensive use and the globalized commerce of agricultural goods, pesticides have become a global concern. Despite the undoubtful advantages of their use in agricultural practices, their misuse is a threat to the environment and human health. Their analysis in environmental samples and in food products continues to gain interest in the analytical chemistry community as they are challenging matrices, and legal concentration limits are particularly low (in the order of ppb). In particular, the use of solid-phase microextraction (SPME) has gained special attention in this field thanks to its potential to minimize the matrix effect, while enriching its concentration, allowing very low limits of detection, and without the need of a large amount of solvents or lengthy procedures. Moreover, its combination with gas chromatography (GC) can be easily automated, making it a very interesting approach for routine analysis. In this review, advances and analytical strategies for the use of SPME coupled with GC are discussed and compared for the analysis of pesticides in food and environmental samples, hopefully encouraging its further development and routine application in this field.