Multicomponent materials with ordered nanoscale networks are critical for applications ranging from microelectronics to energy conversion and storage devices which require charge transport along 3-dimensional (3D) continuous pathways. The network symmetry can facilitate additional properties such as macroscopic polarization for piezoelectric, pyroelectric, and second-order nonlinear optical properties in non-centrosymmetric morphologies. Although pure block copolymers are able to form multiple network morphologies, network tunability remains a challenge for coassembled systems. Here we report the coassembly of niobia nanoparticles with a poly(isoprene-b-styrene-b-ethylene oxide) (ISO) which resulted in multiple network morphologies, one of which was chiral and non-centrosymmetric. Detailed small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) measurements were most consistent with the alternating gyroid (G A) morphology at low nanoparticle loadings and a transition to a centrosymmetric network morphology at higher loadings. This is the first report of multiple network morphologies from coassembly with a single polymer over a ∼10 vol% composition range. The nanoparticle spatial distribution was tomographically reconstructed. Nanocomposite calcination resulted in mesoporous networks. This general approach was further demonstrated with amorphous and anatase titania. © The Royal Society of Chemistry 2011.