•Migration testing of food packaging materials.•GC-MS analysis of caprolactam (regulated additive) and 2,4-di-tert-butylphenol (NIAS).•Method application to real food packaging material.•Salinity level of food simulants may influence migration of analytes from packaging. Caprolactam and 2,4-di-tert-butyl phenol (2,4-DTBP) are substances typically found in some food contact materials (FCMs). They are known to often migrate into food, and are difficult to analyse in liquid food simulants using GC. In this work a simple salting-out Liquid-Liquid Extraction (SALLE) for the analysis of both substances in water and the official food simulant A (10 % v/v ethanol, Regulation (EU) No. 10/2011) is presented. The method, which included analytical determination by GC-MS, was optimized and validated to ensure sufficient analytical quality. The method’s LOQs allowed the proper quantification of caprolactam at its EU legislative limit (15 mg kg−1). For 2,4-DTBP the method also revealed good sensitivity, although no official limits have been established yet. Linear regression coefficients (R2) were in all cases higher than 0.999, and recoveries ranged from 87 % and 95% for caprolactam and 2,4-DTBP, respectively. Precision was also acceptable, with the RSDs (%) below 12 %. The method proved to be adequate to be used for routine analysis. The presence of salt during migration of caprolactam and 2,4-DTBP was also investigated in this work. Polyamide/polyethylene FCM multilayer films have been tested with water and simulant A, containing different amounts of NaCl (up to 15 % m/v), and applying different migration conditions (temperature and time). The results indicated that salinity plays an important effect on the migration of caprolactam, with the presence of salt reducing its migration in case of water and increasing it in case of simulant A. These preliminary results seem to indicate that migration testing should consider not only the well-known fatty content of a food, but also its salinity content, as it may end up affecting drastically the migration of polar substances.