The aim of this study was to show how volatile organic compounds (VOCs) profiling can be used as a method to identify different environments across a city. To achieve that, we employed several methods. First, we carried out the profiling of VOCs in several different locations. Then we identified the marker compounds and their sources. Air samples were collected from 6 different locations within the Vilnius City centre using thermal desorption (TD) tubes. Samples were analysed using thermal desorption coupled with gas chromatography mass spectroscopy (TD/GC-MS) methodology. Compound identification was performed by the library match using the NIST MS Search 2.0 (2005) mass spectral library. The results show how variation in the levels of different VOCs can distinguish between locations within a relatively small area of 2 km2 depending on different emission sources.