Novel Au-decorated Te hybrids with a tripod-shaped planar microstructure were prepared through a two-step hydrothermal process: the synthesis of Te single crystals and the subsequent self-sacrificial reaction of Te template with HAuCl4. Based on the influences of reaction temperature and solvent compositions on the as-obtained microstructures, a plausible mechanism was proposed to account for the formation of the tripod-shaped Te and Au/Te crystals. The as-prepared Au/Te hybrids have the sensitivity of 6.35 μA/ppb in the electrochemical detection of As(III), which represents the highest sensitivity reported in literature. The Au/Te sensor also has a low detection limit of 0.0026 ppb and could work in complex mixtures containing As(III), Cu(II) and other heavy metal ions, exhibiting excellent selectivity on As(III) and Cu(II) ions. The enhanced electrocatalytic property may be attributed to the synergetic interactions between the noble metal and semiconductor and the presence of a large number of active sites on the hybrids surface.