Poly(2,2′-bipyridine-4,4′-dicarboxamide-co-polydimethylsiloxanes) were cross-linked by coordination with Rh3+ to obtain flexible and stretchable polymer-metal complexes (PMCs). The structure of the PMCs was confirmed by FTIR, UV–vis, CV, and by comparison with similar-in-structure low-molecular weight Rh(III) bipyridine complexes. Upon UV–vis irradiation (λex = 345–354 nm), the obtained Rh(III)-containing PMCs exhibit yellow-red phosphorescence at λem = 672–767 nm and increased lifetime up to τ = 2.44 ms under liquid nitrogen temperature (−196.2°C). The PMCs possess a wide range of elongation at break (up to 672%), tensile strength (up to 7.2 MPa) and self-healing properties with efficiency up to 79% at room temperature and 90% at 100°C (especially for PMCs having Mn = 25,000 of PDMS chain). Thus, the significant rise in phosphorescence intensity and lifetime by 420–430 times (from τ = 5.4–5.8 μs to 2.3–2.4 ms) upon cooling from room temperature to −196.2°C enables these Rh(III)-containing PMCs to act as luminescent thermometers, offering potential for cryogenic technologies in optoelectronics, aerospace applications, and biomedicine where non-invasive temperature monitoring is crucial.