Multi-angular branched ZnO microstructures with rods-shaped tips and nanopushpins with hexagonal cap on top have been synthesized by a simple thermal treatment process of compacted ZnS powder used as starting material and substrate. The structures have been grown at different temperatures (800, 900 and 1000 °C) for 60 min, in a constant nitrogen environment at atmospheric pressure via a catalyst-free process. XRD results of the as-grown products from ZnS powder show a significant reduction in the cubic zincblende phase to the hexagonal wurtzite phase with the increase of treatment temperature, as compared to the bulk value. Post-anneal analyses indicated that the transformation of morphologies of the as-grown structures also depends strongly on the treatment temperature. The proposed method represents an easy and economical way to grow complex structures of ZnO, with a relatively short time, furthermore, without the neediness of use an external substrate to grow. These new and interesting nanostructures have potential in applications such as optoelectronics.