Bundled and self-aligned fibers were obtained by electrospinning blends of polystyrene (PS) and poly (methyl methacrylate) (PMMA) with a hairy-rod polyphenylene-g-polystyrene/poly (a-caprolactone) (PP-g-PS/PCL) copolymer. The self-alignment and bundling characteristics of these electrospun fibers were ascribed to the unique molecular architecture of the conjugated polymer, PP-g-PS/PCL, and its interactions with the solvent and the polymer matrixes used for the electrospinning. The self-alignment and bundling was found to be much more pronounced for PP-g-PS/PCL-PS blend when compared to PP-g-PS/PCL-PMMA blend. Furthermore we found that the degree of self-alignment of the fiber bundles was enhanced by increasing the amount of PP-g-PS/PCL in the blends but the alignment completely disappeared when the solvent dimethylformamide was changed to chloroform.