Organophosphorus pesticides (OPPs), widely known as persistent organic pollutants, are the most popular contaminants in agriculture products in developing countries. The determination of OPPs in complex matrices, such as food, environmental and biological samples, usually requires extensive sample pretreatment. This review focuses on the sorptive extraction techniques applied as sample pretreatment for OPPs in complex matrices, including solid-phase extraction (SPE) and solid-phase microextraction (SPME).