This review is focused on the basic concepts of microsegregation and a fundamental understanding of the formation of positionally ordered LC phases based on micro- and nanophases, interaction parameters and interfaces. Selected examples were chosen from the actual literature to illustrate the concepts. Microsegregation is the basis of classical LC phases and cybotaxis, and most importantly, it paves the way to a huge number of new LC phases. Beside the distinct modes of micellar packing motifs and liquid quasicrystals formed by self-assembly of dendritic molecules, attention is also focused on the specific effects of rigid anisometric units and polyphilicity. Honeycomb LC phases, vesicular LC phases and mesophases with 3D-lattices lead to enhanced complexity of LC self-assembly.