The morphologies of blends from a poly(isoprene- styrene-2-vinylpyridine) (ISP) star-shaped terpolymer and a poly(hydroxystyrene-block-methyl methacrylate) (HM) diblock copolymer were studied using transmission electron microscopy (TEM) and microbeam small-angle X-ray scattering (mu-SAXS). Short I homopolymer was added to tune the volume fraction. As for the two parent polymers, P and H chains are very short and naturally form hydrogen bonds. Because of the small P + H complex domain, this blend system can behave like "an ISM star-shaped polymer". By varying the blend ratios of the star and the diblock copolymer, [4.8.8] Archimedean tiling and a new tiling pattern were obtained. ii-SAXS revealed that the new tiling possesses a hexagonal symmetry with large unit lattices beyond the size of a molecule of "the ISM star polymer". Treating the blend films with acetic acid/methanol caused dissociation of the hydrogen bonding and removal of HM, resulting in the porous materials with the specific tiling patterns.