Thin-film samples of titanium phthalocyanine, a sensor of environmental pollutants, were studied by time resolved energy-dispersive x-ray reflectivity (EDXR). This original method demonstrated to be an ideal tool to follow the evolution of the films morphology upon gas exposure, in situ, also allowing an unexpected response of the sensors to be detected. Indeed, while the increase in thickness showed the characteristic feature of a “breathing-like” expansion, already observed in other metal-Pc, the curve of roughness versus exposure time exhibited a peak. This effect, in some cases evident by observation with the naked eye the EDXR data, was attributed to a surface structure rearrangement process.