Pesticides are chemical substances widely used to control, prevent, or eliminate pests in agriculture, gardening, and other sectors. However, their use poses risks to human health, and recent regulatory efforts have focused on minimizing exposure and monitoring residue levels. In this study, the separation of seven pesticides was investigated using supercritical fluid chromatography coupled to diode-array detection (SFC-DAD). The influence of six different stationary phases and various organic modifiers, as well as additional parameters such as temperature, pressure, and the presence of additives, was systematically evaluated to optimize the chromatographic conditions. The best separation performance was achieved using a LiChrospher^® 100 DIOL column with methanol as the organic modifier under a gradient program. Analyses were carried out at a flow rate of 3 mL/min, a column temperature of 35 °C, and a system back pressure of 150 bar, resulting in a total analysis time of approximately 4 min. The optimized method allowed for a faster separation of the selected agricultural pesticides by SFC-DAD compared to conventional chromatographic techniques.