PLL-PEG-PLL was synthesized by deprotection of the amino group of PLL(Z)-PEG-PLL(Z). The properties of the polyion complex (PIC) micelles comprising of PLL-PEG-PLL and DNA were investigated. The results showed that the core of PIC was formed by PLL and DNA through electrostatic interactions, and PEG was shell of PIC, so PIC micelles in aqueous medium were homogenous with no precipitation even under the neutral condition, and PIC had the characteristic of stability, which were very important in gene therapy. At the same time, the results showed PLL-PEG-PLL could condense DNA, longer PLL blocks were generally more effective at condensation, and the nuclease resistance of DNA was increased remarkably. PIC was spherical with diameter of 10―35 nm, which could be easily taken up by cells. Transfection experiments in vitro showed that the DNA encapsulated could be expressed in the cell line SF9.