Poor compatibility was the major drawback of polymer mixtures when used as DNA separation media. Using poly(ethylene oxide)-b-poly(N, N-dimethylacrylamide) (PEO(44)-b-PDMA(88)) and PEO (M(w): 1.3 MDa) as an example, we demonstrated the concept that the compatibility was significantly improved when mixing a homopolymer with its copolymer. Laser light scattering indicated that the major interaction between PEO and PEO-b-PDMA in dilute solution was the weak hydrodynamic interaction, which showed almost no effect on the viscosity and the static scattering pattern. In semidilute or concentrated solution, viscosity measurement also suggested good compatibility between the two components. When tested as DNA separation medium by CE, the viscosity of the mixture was extremely low, only 5 cP for 5.0 m/v% PEO-b-PDMA+0.1 m/v% PEO at 25 degrees C. The performance on DNA separation could be tuned by varying the concentration of each component as well as the component ratio. Good separation on both dsDNA and ssDNA was achieved.