The effects of the oxygen mole fraction on the static properties of pressure-sensitive paint (PSP) were investigated. Sample coupon tests using a calibration chamber were conducted for poly(hexafluoroisopropyl methacrylate)-based PSP (PHFIPM-PSP), polymer/ceramic PSP (PC-PSP), and anodized aluminum PSP (AA-PSP). The oxygen mole fraction was set to 0.1–100%, and the ambient pressure (Pref) was set to 0.5–140 kPa. Localized Stern–Volmer coefficient Blocal increased and then decreased with increasing oxygen mole fraction. Although Blocal depends on both ambient pressure and the oxygen mole fraction, its effect can be characterized as a function of the partial pressure of oxygen. For AA-PSP and PHFIPM-PSP, which are low-pressure- and relatively low-pressure-type PSPs, respectively, Blocal peaks at PO2ref<12 kPa. In contrast, for PC-PSP, which is an atmospheric-pressure-type PSP in the investigated range, Blocal does not have a peak. Blocal has a peak at a relatively high partial pressure of oxygen due to the oxygen permeability of the polymer used in the binder. The peak of SPR, which is the emission intensity change with respect to normalized pressure fluctuation, appears at a lower partial pressure of oxygen than that of Blocal. This is because the intensity of PSP becomes quite low at a high partial pressure of oxygen even if Blocal is high. Hence, the optimal oxygen mole fraction depends on the type of PSP and the ambient pressure range of the experiment. This optimal value can be found on the basis of the partial pressure of oxygen.