In this work, metal free and zinc tetraphenylporphyrin films were employed as nitrogen dioxide (NO₂) gas sensors. The films were vacuum evaporated and the sensor response was evaluated as changes in the optical absorption spectra, hydrophobic properties and conductivity at different gas concentrations. From UV-Vis results, important changes in the absorption peaks were observed after gas exposure. The morphology of the films before and after gas interaction was obtained by using scanning electron and atomic force microscopy. The films morphology showed a degradation after gas adsorption for the metal free system but gas entrapment for the zinc porphyrin film. In order to elucidate the gas adsorption phenomena, density functional theory calculations were also performed. Here, it was observed that the porphyrin chemical structure not only affects the gas coordination sites which affect the porphyrin electronic distribution and packing arrangement, but also, determines the gas detection mechanism for sensing applications.