Results from a five month monitoring campaign of BTX (benzene, toluene and the sum of ethyl benzene, o-xylene, m-xylene and p-xylene), performed at Monterotondo, a little town 23 km NE of Rome, and correlation of the measured concentrations with meteorological and natural radioactivity data are presented and discussed. This campaign allowed us to extrapolate a pattern of the annual distribution of benzene in the town. A map, showing the average distribution of pollutants, is presented, as a useful tool to manage an appropriate policy of air pollution. A contemporary indoor–outdoor investigation has been performed at five homes and two classrooms of Monterotondo and at thirteen homes and thirteen classrooms in the outskirts of Rome. Non-smoking people and low polluted sites were chosen for this campaign, in order to highlight if commonly used domestic materials could act as internal sources. Data, obtained by employing long-term diffusive samplers, are compared with a parallel experiment showing the day–night indoor–outdoor trend. The obtained results, confirmed through statistical analysis of data, let us conclude that there is evidence of internal sources at homes whilst, in the schools, depletion phenomena prevail, probably due to the walls adsorption.