A simple solution chemical route for bulk synthesis of hand-like Bi2O3 microcrystals has been demonstrated. The microcrystals are assembled by several short rods that have a diameter in the range of 50-500 nm, and a length in the range of 1-20 μm. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) were employed to characterize the structure and morphology of these novel structures. The field emission of the sample started at a turn-on field of 2.1 V/μm at a current density of 0.1 μA/cm2, while the emission current density reached about 0.1mA/cm2 at an applied field of 5.5 V/μm. These results suggest that hand-like Bi2O3 microcrystals can be an excellent FE material candidate.