In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84-100 % of the total PAH mass detected.