There has been growing interest in developing new semiconducting polymers for applications in optoelectronics (OLEDs) due to their exceptional processability and appealing characteristic of manipulating electronic and optical properties by tuning of molecular structure and self-assembling. This study is an investigation on the interplay among supermolecular organization and optical properties of thin films of the poly[2-(2-ethylhexyloxy)-5-methoxy]-1, 4-phenylenedifluorovinylene (MEH-PPDFV) conjugated polymer, which has fluorinated vinylene units. This interplay is elucidated exploiting atomic force microscopy, spectroscopy ellipsometry, photoluminescence and electroluminescence. Thin films of MEH-PPDFV have been deposited by drop casting on indium-tin-oxide (ITO), quartz and glass substrates. The dependence of polymer chains self-organization and morphology on substrate surface is presented. Furthermore, it is demonstrated that the presence of F-atoms in the vinylene units of the MEH-PPDFV yields a blue optical band gap with the maximum of the fundamental HOMO-LUMO transition at 331 nm and photoluminescence at 458 nm. The OLED built with the above polymer shows a very stable blue-greenish electroluminescence that is also achieved at 504 nm.