Abstract: Exploring self-assembled nanostructures with controllable architectures has been a central theme in nanoscience and nanotechnology because of the tantalizing perspective of directly integrating such bottom-up nanostructures into functional devices. Here, the growth of kinked single-crystal In2O3 nanostructures consisting of a nanocone base and a nanowire tip with an epitaxial and defect-free transition is demonstrated for the first time. By tailoring the growth conditions, a reliable switching of the growth direction from [111] to [110] or [112] is observed when the Au catalyst nanoparticles at the apexes of the nanocones shrink below approximate to 100 nm. The natural formation of kinked nanoarchitectures at constant growth pressures is related to the size-dependent free energy that changes for different orientations of the nanowires. The results suggest that the mechanism of forming such kinked nanocone-nanowire nanostructures in well-controlled growth environment may be universal for a wide range of functional materials.