An efficient and easy sample pretreatment methodology was proposed for the detection of photoinitiator 4‐methylbenzophenone from milk before high‐performance liquid chromatography. Appropriate conditions for demulsification were studied. The parameters affecting cloud point extraction, such as concentration of Tween‐20, electrolyte salt, equilibration temperature, and time, have been investigated. When the spiked level was 200–1000 μg/kg, the average addition standard recovery was 99.14–105.98% with the optimum cloud point extraction conditions (concentration of Tween‐20, 138 g/L; mass of anhydrous sodium sulfate, 0.75 g; equilibration temperature, 65°C; equilibration time, 30 min). To decrease the detection limits, further work about the organic solvent, shaking time, and ultrasonic parameters was carried. When the spiked level was 10–100 μg/kg, the average addition standard recovery was 70.40–106.91% with the optimum cloud point extraction and enrichment conditions (optimum cloud point extraction conditions; volume of cyclohexane, 30 mL; shaking time, 20 min; time of ultrasonic, 20 min; temperature of ultrasonic bath, 45°C).