The isotropic-liquid crystalline transition of concentrated DNA solutions is investigated using freeze-fracture electron microscopy in order to understand the first steps of the DNA condensation process. Between the isotropic liquid and the cholesteric mesophase, we report the existence of double twist DNA bundles and describe their long range ordering into 3D networks. This organization corresponds to the formation of ‘blue phases’ already observed in thermotropic liquid crystals, but never reported in lyotropic systems. In addition, the size of the DNA molecule, about ten times that of most thermotropic materials, allows here the molecular resolution imaging of blue phase structures. Since such structures recall chromatin organization of some Procaryotes and lower Eucaryotes, we suspect that they may be widespread and of potential interest in the regulation of chromatin functions.