An in situ energy dispersive x-ray reflectivity technique was used to study the morphological changes of gas sensing thin films of ruthenium phtalocyanine (RuPc)2 induced by gas absorption/desorption processes. The time-resolved collection of reflectivity spectra during the exposure of each film to a gas flux of nitrogen oxides provided the evolution of the morphological parameters (thickness and roughness). The gas absorption process develops in two stages: The first induces morphological changes characteristic of a surface (adsorption) process, while the second is dominated by a bulk effect. This two-step behavior is also observed in the desorption process: When the thermal treatment is performed at 130 °C, the gas is released from the bulk only. Conversely, at higher temperatures, the gas is fully released, i.e., also from the surface, and the initial film thickness is regained. Finally, a further in situ study upon a second absorption treatment was carried out: In this case, only the film bulk diffusion process takes place.