This article describes the production and characterization of cationic microparticles based on pullulan and starch for the delivery of nucleic acids. The microparticles were prepared by chemically cross-linkinking of a polymer solution dispersed in organic phase, followed by amination with N, N-diethyl-2-chloroethyl amine hydrochloride, or N-glycidyl-N,N-dimethyl-N-methylammonium chloride. The association of desoxyribonucleotide (DNA) with positively charged microparticles was determined. The association capacity and the affinity of microspheres for DNA were investigated as a function of type of polysaccharide, content and basicity of the amino groups. It was found that the both types of carriers synthetized display a high affinity for defibrotide due to the high porosity of polysaccharide microspheres (PMs). The in vitro release kinetics from microspheres showed an initial fast release of DNA (30 min) followed by slower release rate over 14 days. DNA release was influenced by the ionic strength of the receiving fluid. In addition, DNA release was slightly more rapid from pullulan than from starch complexes. DNA stability studies were performed by agarose gel, indicating no degradation even after 14 days. All the produced cationic microspheres were able to quantitatively load DNA. The release of DNA from PMs was strongly affected by the ionic strength of the receiving fluid. Finally, agarose gel electrophoresis of DNA released from microspheres indicated that no DNA degradation occurs even after 14 days of release from PMs.