The optimum performance of an optical oxygen sensor based on polysulfone (PSF)/[Ru(II)- Tris(4,7-diphenyl-1,10-phenanthroline)] octylsulfonate (Ru(dpp)OS) was checked by carefully tuning the parameters affecting the membrane preparation. In particular, membranes having thickness ranging between 0.2 and 8.0 µm with various luminophore concentrations were prepared by dip-coating and tested. The membrane thickness was controlled by tuning the solution viscosity, and was measured both by secondary ion mass spectrometry (SIMS) and by visible spectroscopy (Vis). Luminescence-quenching-based calibration was a single value of the Stern–Volmer constant (KSV) for membranes containing up to 20 mmol Ru(dpp) g−1 PSF (1.35 µm average thickness). The KSV value decreased for larger concentration. The highest sensitivity was obtained with membrane thickness around 1.6 µm, having a response time close to 1 s. Thicker membranes exhibited an emission saturation effect and were characterized by longer response time. The KSV behavior was interpreted on the basis of a mathematical approach accounting for the contribution of luminescence lifetime, oxygen diffusion coefficient (DO2 ) and oxygen solubility inside the membrane (sO2 ) establishing the role of all of them and allowing their experimental determination. Moreover, a simple experimental way to estimate KSV without needing calibration was proposed. It was based either on the light emission asymmetry or on the percent variation of light emission on passing from pure nitrogen to pure oxygen.