Pesticides are multiple chemical compounds commonly used in agriculture and other sectors to control pests and improve crop productivity. However, their widespread use poses significant risks to human health and the environment, prompting increased regulatory scrutiny and the need for efficient and reliable analytical methods to monitor their residues in various matrices. In this study, a rapid and selective analytical method was developed for the separation of seven commonly used agricultural pesticides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) using supercritical fluid chromatography (SFC) coupled with photodiode array detection (PDA). The method optimization involved the evaluation of six different stationary phases and various organic modifiers, along with parameters such as column temperature, backpressure, and the presence of additives to enhance separation efficiency. The best results were achieved using a Lichrosphere 100 Diol column with methanol as the organic modifier in gradient mode, a flow rate of 3.0 mL/min, a temperature of 35 °C, and a backpressure of 150 bar. Under these optimized conditions, all analytes were successfully separated in less than 4 minutes. The proposed method demonstrates excellent potential for high-throughput screening of pesticide residues in agricultural samples, offering a balance of speed, resolution, and environmental sustainability aligned with green analytical chemistry principles.