Oxygen‐sensitive and near‐infrared (NIR) luminescent YbIII coordination polymers incorporating ligands based on pyrene derivatives were synthesized: YbIII–TBAPy and YbIII–TIAPy (TBAPy: 1,3,6,8‐tetrakis(p‐benzoate)pyrene; TIAPy: 1,3,6,8‐tetrakis(3,5‐isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X‐ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of YbIII–TIAPy has been evaluated by measuring its N2 adsorption isotherm. The NIR luminescence properties of YbIII–TBAPy and YbIII–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. YbIII–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen‐sensing characteristics. These results suggest that NIR luminescent YbIII coordination polymers prepared using pyrene derivatives could have applications in novel thermo‐stable oxygen sensors.