We examine the structure of aggregates formed due to DNA interaction with dipalmitoylphosphatidylcholine (DPPC) in presence of Ca 2+ and Zn 2+ using small-angle synchrotron X-ray diffraction (SAXD) and neutron scattering (SANS). SAXD shows structural heterogeneity as a function of the cation concentration and temperature: At low cation concentration (~1 mM), aggregates show two DPPC phases, one with a lateral segregation of DNA and cation, while higher cation concentration improves the DNA packing and the condensed lamellar phase is observed in DNA+DPPC+20 mM ion 2+ aggregates. The SANS detected the dissolution of the condensed lamellar phase into unilamellar DPPC+Zn 2+ vesicles due to gel → liquid-crystal phase transition in DNA+DPPC+20 mM Zn 2+ aggregates with the short fragmented salmon sperm DNA.