Well-aligned zinc oxide microrod and microtube arrays with high aspect ratios were fabricated on zinc foil by a simple solution-phase approach in an aqueous solution of ethylenediamine (en). The shape of the ZnO microstructures can be easily modulated from rods to tubes by adding cetyl trimethyl ammonium bromide (CTAB) into the reaction system. Control experiments demonstrate that some reaction parameters, such as the concentration of ethylenediamine, the kind of surfactant, reaction time, and the temperature, all have direct influences on the morphology of the products. Based on the early structure arising from arrested growth (nanosheets), a reasonable mechanism for the growth of ZnO microrods and microtubes has been proposed. The products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence emission.