Studies of the chemical composition of atmospheric aerosols, rain water and snow in various regions of the globe quite often show the presence of pyridine and a number of its low mass derivatives. Nevertheless, the sources of those compounds in the environment have not yet been established and definitely require elucidation, supported by reliable experimental results. In the present work the chemical composition of peat combustion products as one of the important sources of atmospheric aerosol emission is studied by two-dimensional gas chromatography – high-resolution mass spectrometry with a focus on the detection of pyridine derivatives. Twenty-five compounds of this class were reliably identified and quantified in laboratory experiments on peat burning. Among them 3-hydroxypyridine predominates, while the rest analytes are mostly represented by alkyl derivatives: pyridine, 2-methylpyridine, 3-methylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2-ethylpyridine, lutidines (in order of decreasing concentration). The distribution of these combustion products coincides with that obtained earlier in environmental studies carried out in Arctic, Central Russia and France. The experiments on peat thermal decomposition by pyrolysis GC-MS demonstrated that the maximum concentrations as well as the number of detected analytes were found under conditions of oxygen lack and a temperature of about 500 °C, i.e. characteristic conditions of peat wildfires. The observed levels of pyridines’ emission recalculated on the peat dry weight exceeded 200 mg kg−1. Considering hundreds of millions tons of peat burning in megafires over 20,000 tons of pyridines penetrate the Earth atmosphere annually. The obtained results allow concluding that peat burning may be the major and still underestimated source of pyridine and lower alkylpyridines in the Earth atmosphere.