The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks,hold asignificant place in ordered nanoscale morphologies for their potential applications as photonic crystals,m etamaterials and templates for porous ceramics and metals.Here,wereport the first alternating network cubic liquid crystals.T hey form through self-assembly of X-shaped polyphiles,w here glycerol-capped terphenyl rods lie on the gyroid surface while semiperfluorinated and aliphatic sidechains fill their respective separate channel networks.This new self-assembly mode can be considered as at wo-color symmetry-broken double gyroid morphology,p roviding at ailored way to fabricate novel chiral structures with sub-10 nm periodicities using achiral compounds.New routes to chirality from initially achiral systems are of particular contemporary interest for obtaining chiral templates in asymmetric synthesis and catalysis. [1] This is important for the use in different fields of material-and nanoscience [2] as well as for the understanding of fundamental principles of the emergence of biological homochirality. [3] Creating chirality in liquids and liquid crystals (LCs), having no fixed positions of individual molecules,i se specially challenging. [4,5] Nevertheless,i tw as recently achieved by mirror symmetry breaking through synchronization and locking-in of transient chiral conformations and configuration. [6] Here we report anew approach to spontaneous generation of chirality based on nano-phase segregation. In the reported case,b reaking the inherent mirror symmetry of the double gyroid cubic phase (Ia " 3d,Q230), known from lyotropic [7] and thermotropic liquid crystals (LCs) [8] (Figure 1a), is achieved by self-assembly of X-shaped polyphilic molecules with two different chains at opposite sides of ar od-like molecular core. [8b] Thecores organize along the gyroid minimal surface, forming aw all that separates the two enantiomeric infinite networks involving these chains.N ano-phase separation of the two poorly compatible semiperfluorinated and aliphatic side-chains,i nto their own networks (blue and red in Figure 1b), gives rise to agyroid cubic phase with two chemically non-equal networks (the "single gyroid" I4 1 32, Q214). This structure has broken mirror symmetry and represents the first alternating network gyroid cubic LC,a nd the first LC with chirality solely based on phase separation. Previous attempts to produce asingle gyroid structure were based on replication from butterflyw ings, [9] lithography [10] and templating. [11] The alternatingd ouble network gyroid wasf ound in narrow compositionr anges of multiblock copolymer blends, [11, 12] leading to structures in the > 100 nm range in allc ases.T he new concept reportedh erein providesat ailoredw ay to fabricate chiral structures withm uch smaller sub-10 nm periodicities, which are of great potential in nano-templating and as enantiospecific membranes for use in enantiomer separation.Supportinginformation and the O...