In this study, a comprehensive derivatization strategy for biogenic amines based on the formation of volatile carbamate derivatives using 2,2,2-trifluoroethyl chloroformate (TFECF) was successfully developed and evaluated. A series of biogenic amine derivatives was obtained in excellent yields (94–99%) and structurally confirmed using NMR, MS, and crystal structure analysis. The reagent demonstrated high reactivity toward primary and secondary amines, providing derivatives of excellent purity and satisfactory volatility. The applicability of the proposed procedure to real food matrices was demonstrated using GC-MS. The obtained results were compared with the corresponding ethyl chloroformate (ECF) derivatives. TFECF derivatives exhibited significantly improved volatility, reflected in shorter retention times and enhanced analytical performance.