Poly(2-vinylpyridine-g-styrene)s were prepared by successive coupling reactions of polystyryl anion and poly-2-vinylpyridinyl anion prepared by anionic polymerizations, with trifunctional coupling agent, trisbromomethylbenzene. Five samples were prepared and characterized. Their volume fractions of polystyrene graft, phi(s), were determined to be 0.24, 0.34, 0.45, 0.58 and 0.67, respectively. Morphologies of the solvent-cast films of the samples were observed by transmission electron microscopy and small-angle X-ray scattering. It was revealed that two samples, with phi(s) of 0.24 and 0.34, show cylindrical structures, while the other three samples have alternating lamellar structures.