It is said that polymer modified asphalt using polyethylene as modifier would show phase separation due to density difference and incompatibility between asphalt and polyethylene. In this study, to prevent coalescence of polyethylene in asphalt, we employed peroxides as phase separation inhibitor. On microscope, peroxides (dicumyl peroxide, lauroyl peroxide) with waste vinyl (comprising low density polyethylene) did not show phase separation, however, rheometer test showed phase separation at molecular level, i.e., polyethylene and asphalt are immiscible ultimately. Mechanical properties (tensile strength, Marshall stability, dynamic stability) showed waste vinyl-modified asphalts are highly resistant to plastic deformation and these properties are even better than those of Superphalt.