Pencil-like ZnO microrods was synthesized via a simple solvothermal process in an aqueous solution of ethylenediamine and ethanolamine. The as-prepared ZnO was characterized by X-ray powder diffraction, field-emission scanning electron microscopy, room temperature photoluminescence spectra and UV–vis absorption spectra. The results indicated that ZnO microrods had the length in the range of 1.3–25 μm. The photocatalytic activity was studied by degradation of methylene blue (MB) aqueous solution, which showed that the as-prepared ZnO microrods possessed a high photocatalytic activity. The formation mechanism of the pencil-like ZnO was also investigated based on the experimental results.