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Composite materials with different concentration ratios of a hybrid of zero-dimensional (0-D) Cs4PbBr6 perovskite, which acts as a donor (D), and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), which acts as an acceptor (A), were successfully prepared via a solution blending method prior to being deposited onto glass substrates by a spin-coating technique. The influence of acceptor content on the structural, optical, and energy transfer properties of the donor was investigated. The perovskite nanocrystals formed thin films without any chemical interactions within a matrix of MEH-PPV in the blend. The possibility of dipole–dipole (non-radiative) energy transfer from the 0-D Cs4PbBr6 to the MEH-PPV was proven. The energy transfer parameters such as Ro (critical distance of the energy transfer), kapp (apparent quenching constant), ∅ D A (quantum yield of D in the presence of A), τ D A (lifetime of D in the presence of A), PDA (probability of energy transfer), η (efficiency of energy transfer), RDA (energy transfer radius), kET (energy transfer rate constant), TDR (total decay rate), Ao (critical concentration of A), and Aπ (conjugation length) were calculated based on the absorption and emission measurements. [ABSTRACT FROM AUTHOR]