Here, a new idea was proposed for template-free synthesis of hierarchical m-ZrO2 nanorods and “their” possible formation mechanism based on a series of chemical reactions by simple hydrothermal method. The traditional preparation methods of hierarchical ZrO2 nanorods involved inexpensive equipment, complicated process, and high production cost. The as-synthesized products composed of many nanorods with 180-200 nm in diameter and 5-7μm in length. The ifnal product after annealing involved hierarchical monoclinic ZrO2 (m-ZrO2) nanorods, namely, the big nanorod was made up of many small nanorods with 40-50 nm in diameter and 500-600 nm in length. The experimental results were useful in understanding the chemical properties of ZrB2 and ZrO2 and the design of the derivatives for m-ZrO2 nanomaterials.