Objectives: The study objective was to assemble emission characteristics of the sources of the ambient volatile organic compounds (VOCs) and to elaborate methods of organizing them into the sources’ chemical profiles. Material and Methods: The UNMIX – sensor modeling method from the U.S. Environment Protection Agency (EPA) – was used to process the VOC concentration data acquired over the years 2000–2009 for 175 VOC species in 4 air quality monitoring stations in Montreal, Quebec. Results: The method enabled to assess VOC emissions from the typically distributed sources existing in urban environment and VOC occurrences characterizing the local, or point-like, sources. The distributed sources were inextricably associated with hydrocarbons from exhaust, heavier hydrocarbons from contaminated urban soil, fugitive evaporations of gasoline and liquefied petroleum gases (LPG), leakage from the industrial and commercial use of solvents, and the inert, ozone depleting gases permeating urban atmosphere. The sources’ profiles were charted involving 60–120 VOC species per source. Spatial distribution of the sources was examined. Conclusions: The UNMIX application and the source profiling methods, by building robust chemical profiles of VOC sources, provided information that can be used to assign the measured VOC emissions to physical sources. This, in turn, provides means of assessing the impact of environmental policies, on one hand, and of industrial activities on the other hand on VOC air pollution.