Designed ZnII and CrIII porphyrins (ZnIIP, CrIIIP(Cl)(H2O)) and conventional ZnIITPP and CrIIITPP(Cl)(H2O) are immobilized into porous polysiloxane films via chemical vapor deposition enhanced by an atmospheric pressure dielectric barrier discharge. UV/vis spectroscopy and mass spectrometry prove the integrity of the chromophores after the plasma treatment. The optical amine sensing capabilities of the films are investigated spectroscopically on exposure to triethylamine vapors. A series of coatings with different porphyrin loadings indicate influences of the deposition conditions on the growth of the sensing films and hence the device performance. Additionally, the synthesis and characterization of the novel porphyrin complex CrIIIP(Cl)(H2O) is reported.