In the vicinity of metal nanostructures, phosphorescent intensity can be greatly enhanced through the localized surface plasmon resonance (LSPR). The enhancement of phosphorescence intensity in noble-metal nanoparticle (NP) systems is highly dependent on the overlap of the absorbance peak of a noble metal with that of phosphorescent dyes. When the peak of the NPs’ absorption spectra has a maximum overlap with that of these dyes, the phosphorescence enhancement is the largest. Here, we use a seeded growth method to synthesize SiO2/Au NPs with tunable plasmonic resonance and compare their phosphorescence enhancement for an oxygen range of 0–21%. The measurement sensitivity of oxygen is strongly dependent on the enhancement of phosphorescence. When used with PtTFPP, when the absorbance peak of the SiO2/Au NPs has a maximum overlap with that of PtTFPP, the phosphorescence enhancement factor is as high as 7; the sensitivity of oxygen concentration is as high as 75. Moreover, we also optimize the performance by varying the number of NPs to eliminate the nonradiative energy-transfer (NRET) process and self-quenching.