This paper reports a method to produce networks of crystalline gallium oxide comprised of one-dimensional (1D) nanostructures. Because of the unique arrangement of wires, these crystalline networks are termed as ‘nanowebs’. Nanowebs are of great technological interest since they contain wire densities of the order of 109 cm–2. A possible mechanism for the fast self-assembly of crystalline metal oxide nanowires involves multiple nucleation and coalescence via oxidation–reduction reactions at the molecular level. The preferential growth of nanowires parallel to the substrate enabled them to coalesce into regular polygonal networks. The individual segments of the polygonal network consist of both nanowires and nanotubules of β-gallium oxide. Individual wire properties contribute to a nanoweb’s overall capacity and the implications for devices based on nanowebs are expected to be enormous.