Considering the increase of atmospheric pollution levels in our cities, due to emissions from vehicles and domestic heating, and the growing threat of terrorism, it is necessary to develop instrumentation and gather know-how for the automatic detection and measurement of dangerous substances as quickly and far away as possible. The Multi- Wavelength DIAL, an extension of the conventional DIAL technique, is one of the most powerful remote sensing methods for the identification of multiple substances and seems to be a promising solution compared to existing alternatives. In this paper, first in-field tests of a smart and fully automated Multi-Wavelength mini-DIAL will be presented and discussed in details. The recently developed system, based on a long-wavelength infrared (IR-C) CO2 laser source, has the potential of giving an early warning, whenever something strange is found in the atmosphere, followed by identification and simultaneous concentration measurements of many chemical species, ranging from the most important Greenhouse Gases (GHG) to other harmful Volatile Organic Compounds (VOCs). Preliminary studies, regarding the fingerprint of the investigated substances, have been carried out by cross-referencing database of infrared (IR) spectra, obtained using in-cell measurements, and typical Mixing Ratios in the examined region, extrapolated from the literature. First experiments in atmosphere have been performed into a suburban and moderately-busy area of Rome. Moreover, to optimize the automatic identification of the harmful species to be recognized on the basis of in cell measurements of the absorption coefficient spectra, an advanced multivariate statistical method for classification has been developed and tested.