Polystyrene-polyarylate (PS-PAr) block copolymer was applied as a moldability modifier of polycarbonate (PC). From the 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) extraction results, PS-PAr block copolymer was demonstrated to copolymerize with PC via an in situ reaction between the PAr chain and PC. As a result of the chemical bonding between PS and PC chains, the PS dispersed domain in the PS-PAr block copolymer/PC blend could be reduced, on average, to a size smaller than the visible light wavelength. In particular, by adjusting PAr composition to 30 wt % in the fed PS-PAr block copolymer during the melt-mixing process, the PS domain size was completely reduced to be smaller than the visible light wavelength. As a result the blend substrate could satisfy the transparency required for the optical disk substrate with higher memory density: homogeneity under polarizing light, clarity on the reflective plate, and transparency at 400 nm. The melt viscosity could be lowered to the equal viscosity level of PC at about 30°C higher temperature by blending PC 15 wt % with the PS-PAr block copolymer. The lowered melt viscosity could reduce the retardation in the optical disk substrate, which was equivalent to that of the PC substrate processed at 30°C higher. In addition, the PS-PAr block copolymer/PC blend could attain the exact groove transcription at 20°C lower mold temperature than that of PC as a result of the lowered elastic modulus caused by the PS-rich phase. These features of the PS-PAr block copolymer/PC blend indicated a potential to offer an improved process window for the substrate molding. Because of its excellent transparency and a potential for processing flexibility, the PS-PAr block copolymer/PC blend would be a promising material for optical disk substrates with higher memory density.