This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cy-cloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N ₃-PDMS) was synthesized for incorporation of azide function in polysilox-ane chain. [Re(CO) ₃ (MeCN)(5-(4-ethynylphenyl)-2,2 ^′-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N ₃-PDMS (Re1-PDMS), while [Re(CO) ₃Cl(5,5 ^′-diethynyl-2,2 ^′-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N ₃-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties.