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Electron emission from polycrystalline diamond particles (PDPs) was obtained at low electric fields in the absence of intentional doping. The PDPs were synthesized on a silicon substrate using microwave-plasma chemical vapor deposition accompanied by bias-enhanced nucleation. Polycrystalline diamond particles of two different sizes, i.e., ∼500 nm and 2 to 5 μm, were obtained, the surfaces of which were covered with small crystal grains composed of fine facets. Electron emission from the PDPs was characterized by Fowler-Nordheim tunneling with low turn-on-field values (0.8 – 2.0 V/μm) and a low barrier height of 0.02 eV. An emission current greater than 5 μA was maintained for over 24 h in a cathode based on the developed PDPs. In contrast, single-crystalline diamond particles prepared for comparative purposes exhibited no emission up to 2.5 V/μm. Auger electron spectroscopy revealed that the surface oxygen content modified by annealing in air did not affect the emission properties. The macroscopic spatial distribution of the emission spots was roughly consistent with the population density distribution of PDPs on the cathode. It is postulated that emission from the PDPs arises as a result of the small crystal grains on the surface and the presence of a sp2-bonded phase in the grain boundaries, which enabled strong field enhancement and carrier transport through the undoped diamond particles.