The morphological properties of four binary blends of polyethylene synthesized by metallocene catalyst(MCPE) and four polyolefins prepared by Ziegler-Natta catalyst have been investigated to interpret the effect of micro-molecular structure on the phase morphology and interfacial behavior; four binary blend systems studied are high density polyethylene(HDPE)-metallocene polyethylene (MCPE), polypropylene(PP)-MCPE, poly(propyleneco-ethylene) (CoPP)-MCPE, and poly(propylene-co-ethylene-co-1-butylene) (TerPP)-MCPE, and they are all phase separated. The HDPE-MCPE blend shows evenly growing homogeneous HDPE domain on the continuous MCPE phase, on the other hand, the rest of three blends show complex heterogeneous phase behavior. The PP-MCPE blend shows that PP and MCPE and completely phase separated and phase inversion takes place at 50% MCPE. The CoPP-MCPE and TerPP-MCPE show enhanced interface due to the same micro-molecular structure of ethylene, and phase inversion takes place at 40% MCPE. In particular, TerPP-MCPE blend shows improved phase morphology between interfaces, and this may be arisen from the comonomer contents in TerPP, which are 1-butene and ethylene having the same chemical structure as that of MCPE. The enhancement of the phase morphology in the TerPP-MCPE blend is correlated with the mechanical and morphological properties. Thus, although the four blend systems are phase separated, the phase morphology suggests that the order of interfacial adhesion strength be HDPE-MCPE > TerPP-MCPE > CoPP-MCPE > PP-MCPE and that micro-molecular structure between constituents be one of major factors giving enhanced interfacial adhesion