Nicotine Polacrilex is a compound that can be used as a nicotine source in nicotine pouches. The compound is the nicotine salt of the resin Amberlite IRP64 that has a weakly acidic character. Amberlite IRP64 is a copolymer of methacrylic acid with 1,4- and 1,3-divinylbenzene. Analysis of nicotine Polacrilex cannot be performed using a procedure that involves its dissolution since Amberlite IRP64 is a crosslinked polymer insoluble in virtually any solvent. The presence of other components of nicotine pouches such as microcrystalline cellulose and maltitol complicates the analysis based on IR or Raman spectroscopy. A pyrolysis-GC/MS technique has been developed and applied for the analysis of nicotine Polacrilex in nicotine pouches. The procedure uses phenanthrene adsorbed on silica as an internal standard. Both qualitative and quantitative analysis of nicotine Polacrilex can be performed using the procedure. Since the level of total nicotine can also be evaluated by the same procedure, from the ratio of total nicotine to that of nicotine Polacrilex it can be determined if all nicotine results from nicotine Polacrilex, or additional sources of nicotine are used in a nicotine pouches sample.