Migration of BPA from polycarbonate has already been extensively studied. Unfortunately, the nature of (other) substances migrating from the polymeric alternatives to polycarbonate is much less known. Therefore, there is an urgent need to assess the risks associated with the migration of (unknown) chemicals from food contact materials, with emphasis on baby bottles. In this context, the use of simulants is prescribed in the legislation to mimic the testing of real foods. Specifically, we selected a 50% (v/v) EtOH in water solution as a simulant for milk. After sterilization of the bottle during ten minutes with boiling water, three migrations were performed during 2h at 70 °C. The principal aim of the study was the identification of major compounds migrating from baby bottles using a liquid-liquid extraction followed by GC/MS analysis. A non-targeted liquid-liquid extraction method with ethyl acetate:n-hexane (1:1), previously optimized with a mixture of 14 commonly migrating organic compounds, was performed on the simulant samples. Identification of migrating chemicals was done by comparing their obtained MS spectra with commercially available WILEY and NIST mass spectra libraries. Generally, clear differences in the migrating compounds and their intensities were observed between the different types of tested plastics and between the same plastic types available from different producers. Differences in the migration patterns were perceived as well between the sterilization and the migrations and within the different migrations. Silicone, Tritan and polypropylene (PP) exhibited a wide variety of migrating compounds, whereas polyethersulphone (PES) and polyamide (PA) showed a lower amount of migrants, though sometimes in relatively large amounts. Alkanes (especially in polypropylene (PP) bottles), phthalates (dibutylphthalate in one PP bottle and one silicone bottle; diisobutylphthalate in one PP, silicone and Tritan bottle), anti-oxidants (Irgafos 168, degradation products of Irganox 1010 and Irganox 1076), etc. were detected for PP, silicone and Tritan bottles. Although the concentrations were relatively low, for some compounds such as e.g. 2,4-di-tert-butylphenol; 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) or 2-butoxyethyl acetate the specified migration limit was exceeded.