Functionalized silica-based thin films, modified with hydrophobic groups, were synthesized and used as sensors for nitroaromatic compound (NAC) specific detection. Their performance and behavior, in terms of stability, ageing and regeneration, have been fully characterized by combining chemical characterization techniques and electron microscopy. NAC was efficiently and specifically detected using these silica-based sensors, but showed a great degradation in the presence of humidity. Moreover, the sensor sensitivity seriously decreases with storage time. Methyl- and phenyl-functionalization helped to overcome this humidity sensitivity. Surface characterization enabled us to establish a direct correlation between the appearance, and increasing amount, of adsorbed carbonyl-containing species, and sensor efficiency. This contamination, appearing after only one month, was particularly important when sensors were stored in plastic containers. Rinsing with cyclohexane enables us to recover part of the sensor performance but does not yield a complete regeneration of the sensors. This work led us to the definition of optimized elaboration and storage conditions for nitroaromatic sensors.