A simple, effective, and environment‐friendly sample preparation method featuring electromembrane extraction followed by high‐performance liquid chromatography analysis was developed for the simultaneous determination of non‐steroidal anti‐inflammatory drugs (indoprofen, ketoprofen, naproxen, and ibuprofen) in human urine. Optimization was performed for parameters such as sample dilution, liquid membrane type, donor/acceptor solution pH, stirring speed, voltage, and extraction time. For spiked samples, the limits of detection and quantitation equaled 0.20–0.27 and 0.68–0.84 μg/mL, respectively, with the accuracy and precision in the working range equaling 95.1–128.4 and 2.71–10.2%, respectively. Linear equations used for quantitative analysis were valid in the concentration range of 0.68–8.4 μg/mL, with correlation coefficients (R) equaling 0.9934–0.9979.