In this paper the use of passive sampling as a powerful approach to monitor atmospheric CO2 is assessed. Suitable substrate based on calcium-aluminium oxide was synthetized according to a process which permits to control the particle size of the CaO/Al based sorbent. The study shows that hydration of substrate is an essential part of the process of CO2 absorption and subsequent conversion to carbonate. X-ray diffraction, thermogravimetric analysis, environmental scanning electron microscopic analysis were used in order to characterize the substrate and to establish the best performances both in terms of particle size and CO2 absorption capacity.Passive samplers for CO2 monitoring were prepared and then tested at laboratory level and in the atmospheric environment. Validation was performed by comparison with an infrared continuous detector. Thermogravimetric analysis results, carried out to evaluate the absorbing capability of this new passive device, were in accordance with data collected at the same time by the active continuous analyser.The diffusive sampling rate and the diffusion coefficient of CO2 respect to this new passive device were also evaluated resulting equal to 47 ± 3 ml min−1 and 0.0509 ± 0.005 cm2 s−1, respectively.