Salting-out-assisted liquid-liquid extraction (SALLE) was developed to extract thiacloprid (THI) from fruits and vegetables. SALLE conditions (NaCl/Na2SO4, pH, and solvent polarity) were investigated at various levels for the optimal recovery of THI. Meanwhile, reverse-phase high-performance liquid chromatographic (RP-HPLC) conditions were balanced over 1-100 mu g/mL of THI. The optimized SALLE-RP-HPLC method offered 78.33-92.00% recovery of standard THI at an acceptable repeatability 1.81-4.30% and reproducibility 1.08-4.74%. The detection and quantification limits were found to be 0.03 and 0.05 mu g/mL, respectively. The real-time analysis verifies its suitability and ease of use for the determination of THI in agricultural commodities.