The current work focused on investigating the Förster resonance energy transfer (FRET) mechanism from the donor, poly[bis(4-butypheny)-bis(phenyl)benzidine] (poly-TPD), to the acceptor, poly[2-methoxy-5-(3,7-dimethyl-octyloxy)-1,4-phenylenevinylene]-end capped with Dimethylphenyl (MDMO-PPV–DMP). The solution blending method was utilized to prepare the poly-TPD/MDMO-PPV–DMP hybrids with various content. The improvement in energy transfer from poly-TPD to MDMO-PPV–DMP with increasing acceptor content was confirmed by analyzing absorption and emission spectra. The efficient energy transfer in the hybrids is evident from the shorter quantum yield and lifetime of the donor in the hybrids compared to those in pure poly-TPD. The parameters that govern FRET, such as Stern–Volmer value (kSV), quenching rate value (kq), Förster radius (R0), distance between the molecules of poly-TPD and MDMO-PPV–DMP (RDA), energy transfer lifetime (τET), energy transfer rate (kET), total decay rate of the donor (TDR), critical concentration (Ao), and conjugation length (Aπ) could be adjusted by increasing the acceptor content in the hybrids. Furthermore, the red shifting of CIE coordinates upon increasing the acceptor content is additional confirmation for the efficient of FRET in the hybrids.