We report the hot-filament chemical vapor deposition (HFCVD) growth of Zn-ZnO core-shell microspheres in the temperature range of 350–650°C only using ZnO pellets as raw material. The samples were characterized by scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD) techniques. SEM micrographs showed the presence of solid microspheres and a Zn-ZnO layer in all samples. The observed heterogeneous morphology on each sample suggested two different growth mechanisms. On the one hand, solid microspheres were formed by means of gas phase nucleation of Zn atoms. The Zn-ZnO layer was formed on the substrate as result of surface reactions. It is possible that Zn microspheres condensed during the natural cooling of the HFCVD reactor as they were observed on the Zn-ZnO layer.