The structural evolution and properties of poly(9,9-dihexylfluorene-alt-2,5-dialkoxybenzene) with different lengths of alkoxy side chains on phenylene have been systematically investigated by means of thermogravimetric analysis (TGA),X-ray diffraction (XRD),differential scanning calorimetry (DSC),polarizing light microscopy (PLM),atomic force microscopy (AFM),and cyclic voltammetry (CV) techniques.The polymer self-organizes into a lamellar structure consisting of both two- and one-layer packing,and the two-layer packing style is the dominant structure.In addition,the two-layer and one-layer packing structures also accompany the presence of planar stacking and/or crystalline and noncrystalline structures,thus maintaining the stability of the packing. PF6OC6 shows three ordered phases (two crystalline phases and one nematic phase) during the heating process.With further increase of the length of alkoxy side chains, only two ordered phases (one crystalline phase and one nematic phase) are observed and the polymers show a melting-recrystallization phenomenon,which is steadily inhibited as the length of the alkoxy side chains increases.The optical and electrochemical properties of the polymers do not exhibit noticeable dependence on the length of the alkoxy side chains.However,the thermal stability,the vibronic structures, and the full width at half-maximum (fwhm) in photoluminescence spectra of the films gradually decrease,and the oxidation onset potentials and the corresponding HOMO energy levels slightly increase with increasing length of alkoxy side chains on phenylene.These results indicate that the length variation of alkoxy side chains does not change the electronic structure of the polymer backbones,but remarkably affects the microphase separation between the flexible side chains and the conjugated backbones.