We have developed the yttrium oxide (YNP) or ytterbium oxide (YbNP) nanoparticle/polymer matrices for the size-dependent separation of DNA ranging from 100 bp to 9,000 bp. High separation efficiency (> $10^6$ plates/m) and the baseline resolution for various DNA standards (100 bp, 500 bp, and 1 kbp DNA ladder) were obtained in 10 min with these matrices. The effects of concentrations of both polyethylene oxide (PEO) and nanoparticles were investigated and the highest performance was obtained at 0.02% PEO with 0.02% YNP or YbNP. Similar sieving power for both YNP and YbNP matrices was observed probably due to the similar sizes of nanoparticles, resulting in the formation of comparable sieving networks for DNA separation. For the reduction of electrosmotic flow, either dynamic or permanent coating of the capillary inner wall was compared and it turned out that PEO was superior to polyvinylpyrrolidone (PVP) or polyacrylamide (PAA) for better separation efficiency.