Per- and polyfluorinated alkyl substances (PFASs) are compounds of concern due to their emission to the environment since they are persistent and potentially bioaccumulative. The regulations and phase-outs of some of these compounds have led to an increase of replacement substances. A gas chromatography-mass spectrometry (GC-MS) method for analyzing five of these new emerging fluorinated substances have been developed together with evaluation of sorbents for air sampling. The five PFASs are 2,5-bis(trifluoromethyl)-3,6-dioxaundecafluorononanoyl fluoride (FMeEth), perfluorotributylamine (PFTBA), perfluoroperhydrophenanthrene (FPh), 3,5‐bis(trifluoromethyl)-bromobenzene (MBT-Br) and bromopentafluorobenzene (BrFBz). A DB-5MS column with a (5%-phenyl)-methylpolysiloxane phase was used for the optimized GC-MS method. Analytical thermal desorption (ATD) was evaluated as an injection system together with three different sorbent tubes (Tenax, Carbotrap 300 and Carbopack X). Another spiked sampling test was conducted with (Tenax TA (poly(2,6-diphenyl-p-phenylene oxide) resin), XAD-2 (2-hydroxymethyl piperidine resin) and PUF (polyurethane foam). The optimized GC-MS method showed good resolution and worked well for the targeted substances. Using ATD as an injection system were not optimized due to time limitations but showed promising results. The most suitable sorbent for air sampling of the target compounds was Tenax TA. This was determined by calculating the recovery during one of the spike sorbent tests and is therefore recommended to be used for air sampling of the target compounds.