We report the catalyst-free synthesis of ZnO nanobranches on Si nanowires using metalorganic chemical vapor deposition. The formation of single-crystalline ZnO nanobranches on Si nanowire backbones has been confirmed by lattice resolved transmission electron microscopy. Depending on the growth parameters, especially the growth temperature, the morphology and size of the ZnO nanobranches evolved from nanothorn-shaped (at 350 °C) to nanoneedle-shaped structures (at 500 °C). When the growth temperature was further increased to 800 °C, thin ZnO nanowire branches grew out of the Si nanowire backbones coated with thin ZnO shells, whereas no ZnO branch was formed on bare Si nanowires due to limited nucleation. The growth behavior was further exploited to fabricate ZnO/Si nanowire networks by growing the ZnO nanowires selectively on laterally aligned Si–ZnO core-shell nanowire arrays. In addition, cathodoluminescent properties of ZnO nanobranches on Si nanowire backbones are discussed with respect to position and size.