Biodegradable monomethoxy(polyethyleneglycol)-poly(lactide-co-glycolide)-monomethoxy(poly-ethyleneglycol) (PELGE) copolymers were synthesized by ring-opening polymerization to formulate plasmid DNA loaded nanoparticles. A double emulsion method with polyvinyl alcohol as the emulsifier in the external aqueous phase was employed to prepare nanoparticles. The effects of monomethoxypoly(ethyleneglycol) (mPEG) segments in the polymer on particle size, zeta potential, encapsulation efficiency and in vitro release were investigated. It was found that the introduction of a certain amount of hydrophilic mPEG segments in the copolymer chains could improve the affinity of copolymer with plasmid DNA and enhance the emulsification ability of the copolymer. Thus DNA loaded nanoparticles with smaller particle sizes and higher encapsulation efficiencies were obtained by using PELGE copolymer as the matrix.