To maximize luminescent brightness in organic light-emitting diode (OLED) systems, charge transport dynamics of emissive layer is needed to be controlled. Herein, we pattern aligned micrometer scale conjugated polymer structures using a solution based processing method. Super yellow (SY)-polyethylene oxide (PEO) nanofibers were electrospun using simple uniaxial electrospinning method. A hybrid bilayer of SY-PEO fiber and poly (9,9-dioctylfluorene) derivative PFO film was formed by the sequential deposition of the electrospun fiber and spincoated film. The maximum brightness of hybrid LED devices was increased over 1.7 fold to that of film-film bilayer device possessing same average film thickness. Besides, optical properties such as absorption/luminescence of SY were modulated by the rapid crystallization and solvent evaporation during electrospinning process compared to the spin-coated film. The electroluminescence enhancement and color control was attributed to balanced charge transport and enhanced Forster resonance energy transfer (FRET).