Room temperature phosphorescent oxygen sensors have been designed by embedding symmetric palladium(II) or platinum(II) meso-tetraphenylporphyrins in poly(1-trimethylsilyl-1-propyne) in the form of nanofibers along with/without silver nanoparticles. These materials combine the advantages of the high oxygen sensitivity of porphyrins and the enhanced surface area of porous nanofibers. Phenylacetylide bearing palladium(II) or platinum(II) meso-tetraphenylporphyrins (Pd-TPA, Pt-TPA, Pd-TPP and Pt-TPP) were designed to enhance phosphorescence quantum yields as well as sensitivity towards oxygen. Their syntheses were achieved by 2 alternative methods including successive metallation reactions and Sonogashira coupling via optimization of the synthetic strategies and conditions. The respective effect of the metal (Pd or Pt) and substituent on phosphorescence quantum yield as well as other photophysical properties was considered. The sensing performances of the corresponding silver-free and silver doped nanofibers were tested in the oxygen concentration range of 0.0-100.0%. The offered composites provided the advantages of fast response, enhanced sensitivity, reversible and long lasting response, higher Stern-Volmer constants (KSV) and low limit of detection values extending to 7.5 ppm for oxygen.