Trichloroethylene (TCE) and toluene (TOL), which have been used for (3-cyclodextrin ((3-CD) synthesis, need to be properly inspected for quality assurance and safety of food additives. In this study, a combination of static headspace separation and gas chromatography-mass spectrometry (SH-GC-MS) was optimized for detecting those residual solvents in (3-CD in the compatible safe and green chemistry. Sample injection amount for SH was determined to 100 mu L with the minimum volume that provides the suitable accuracy. For the safety and accuracy of analysis, equilibrium conditions of solvents were considered and selected to 60 degrees C for 45 min. Also, we found that the addition of salt, like CaCl2, adversely affected recovery efficiency. Under the proposed condition, coefficients of determination (R-2) of both TCE and TOL were more than 0.99 between 0.05-10 mg/L concentrations. Recovery rates and relative standard deviation (RSD) of tested solvents were between 91.7-106.0% and 1.0-8.9%, respectively. From validation with two commercial (3-CDs, both TCE and TOL presented lower than regulatory limits for food additives (1 ppm) with satisfactory RSDs (<20%). Collectively, the proposed analytical methods can contribute to safer, simpler, and greener inspection of residual chemicals present in foods for public health.