An optical oxygen sensor based on the phosphorescence quenching of palladium tetrakis(4-carboxyphenyl)porphyrin (PdTCPP) self-assembled film (SAM) on alumina plate was developed. The phosphorescence intensity of PdTCPP film decreased with increasing oxygen pressure, indicating that the film can be used as an optical oxygen-sensing device based on phosphorescence quenching by oxygen. The ratio I0/I100 as a sensitivity measure of the sensing film is estimated to be 17.7, showing that the film is a highly sensitive device for oxygen pressure. The film obeyed Stern–Volmer plots with a multisite model and possessed good operational stability and a fast response. Response times are 36 s for deoxygenated to oxygenated conditions and 148 s for the reverse conditions.