A GC-HRMS analytical method for the determination of 60 migrant substances, including aldehydes, ketones, phthalates and other plasticizers, phenol derivatives, acrylates, and methacrylates, in plastic food contact materials (FCM) has been developed and validated. The proposed method includes migration tests, according to Commission Regulation (EU) 10/2011, using four food simulants (A, B, C, and D1), followed by vortex-assisted liquid–liquid extraction (VA-LLE) and GC-Q-Orbitrap HRMS analysis in selected ion monitoring (SIM) mode, with a resolving power of 30,000 FWHM and a mass accuracy ≤5 ppm. The method was validated, showing satisfactory linearity (R2 ≥ 0.98 from 40 to 400 µg L−1), limits of quantification (40 µg L−1), precision (RSD, 0.6–12.6%), and relative recovery (81–120%). The proposed method was applied to the analysis of field samples, including an epoxy-coated tin food can, a drinking bottle made of Tritan copolyester, a disposable glass made of polycarbonate, and a baby feeding bottle made of polypropylene, showing that they were in compliance with the current European regulation regarding the studied substances.