This work reports a method for extraction and analysis of thiosultap sodium, thiocyclam, and nereistoxin in pepper. Different extraction methods were tested to attain the best recoveries. The final extraction method combines acetonitrile extraction in an acidic medium with ultrasonic extraction followed by a cleanup step with anhydrous MgSO(4). The analyses were performed on a Linear Ion Trap Quadrupole LC-MS/MS in negative mode for thiosultap sodium and in positive mode for thiocyclam and nereistoxin. Recovery studies carried out on peppers spiked at different fortification levels (20 and 200 μg∙kg(-1)) yielded average recoveries in the range 58-87% with RSD (%) values below 20%. Calibration curves covering two orders of magnitude were performed and they were linear over the concentration range studied (0.001-0.5 mg∙l(-1)). Instrumental detection limits were in the low μg∙kg(-1) range. Stability studies of thiosultap sodium in water were performed by evaluating a 100-μg∙l(-1) solution of this compound in water. It was analyzed over 7 days, after which more than 80% degradation of thiosultap sodium could be observed.