Shape selective synthesis of ZnO micropencils and microhexagonal cones has been demonstrated using a controlled method of modified vapor deposition. A plausible growth mechanism based on the results of scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetry, and differential thermal analysis is proposed. Our results suggest that growth of micropencil takes place as per the vapor-liquid-solid progression while the microhexagonal cones grow in two steps following a vapor-solid/vapor-liquid-solid mechanism. Moreover, the geometry, the location of substrate and temperature are found to have key roles in governing the morphology. XPS studies clearly demonstrate the presence of Si species as SiO and SiO2, which act as catalysts enabling nucleating sites for ZnO microstructural growth.