Octahedra of In2O3 have been prepared on the side walls of hexagonal ZnO nanowires using a two-stage vapour-liquid-solid process. Raman studies of In2O3 and ZnO heterostructures show distinct phonon peaks corresponding to cubic In2O3 and hexagonal ZnO. From the room temperature photoluminescence it is found that the strong UV emission of ZnO nanowires has quenched significantly after In2O3 octahedra are grown over them. On the other hand, the emission related to In2O3 in the visible and violet regions is also observed. Growing such heterostructures radially is now one step closer to growing them axially in a single nanowire. (C) 2011 Elsevier B. V. All rights reserved.