Biomimetic polymer nanofibers integrate sensing capabilities creating utility across many biological and biomedical applications. We created fibers consisting of either a poly(ether sulfone) (PES) or a polysulfone (PSU) core coated by a biocompatible polycaprolactone (PCL) shell to facilitate cell attachment. Oxygen sensitive luminescent probes Pt(II) meso-tetra(pentafluorophenyl)porphine (PtTFPP) or Pd(II) meso-tetra(pentafluorophenyl)porphine (PdTFPP), were incorporated in the core via single-step coaxial electrospinning providing superior sensitivity, high brightness, linear response, and excellent stability. Both PESPCL and PSUPCL fibers provide more uniform probe distribution than polydimethylsiloxane (PDMS). PSU-based sensing fibers possessed optimum sensitivity due to their relatively higher oxygen permeability. During exposure to 100% nitrogen and 100% oxygen, PESPCL fiber displayed an I-0/I-100 value of 6.7; PSUPCL exhibited a value of 8.9 with PtTFPP as the indicator. In contrast, PdTFPP-containing fibers possess higher sensitivity due to the long porphyrin lifetime. The corresponding I-0/I-100 values were 80.6 and 106.7 for the PESPCL and PSUPCL matrices, respectively. The response and recovery times were 0.24/0.39 s for PESPCL and 0.38/0.83 s for PSUPCL which are 0.12 and 0.11 s faster, respectively, than the Pt-based porphyrin in the same matrices. Paradoxically, lower oxygen permeabilities make these polymers better suited to measuring higher (i. e., similar to 20%) oxygen contents than PDMS. Individual fiber sensing was studied by fluorescence spectrometry and at a sub-micrometer scale by total internal reflection fluorescence (TIRF). Specific polymer blends relate polymer composition to the resulting sensor properties. All compositions displayed linear SternVolmer plots; sensitivity could be tailored by matrix or the sensing probe selection.