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An alternant poly(dihexyl fluorene-co diphenyl oxadiazole) has been synthetized by microwave-assisted oxidative polymerization. The structure has been confirmed by ¹H-NMR and FTIR spectroscopies. Gel permeation chromatography indicated high molecular weight and low polydispersity index. DFT calculations suggested a complete separation of HOMO and LUMO orbitals, which were located on fluorene and oxadiazole moiety, respectively. X-ray diffraction, polarized light microscopy, and atomic force microscopy indicated the polymer tendency to stack into a layered morphology with a more compact structure for the films prepared by spin coating. Furthermore, UV-vis and photoluminescence spectroscopies indicated the formation of H-aggregates which played a key role in photoluminescence quenching in solid state. Nevertheless, the good charge mobility gained due to the orbital overlapping in H-aggregates led to excellent electroluminescence, which enabled the development of white OLED devices with outstanding stability.