Photoemission-assisted plasma-enhanced chemical vapor deposition (PA-PECVD), a process in which photoelectrons emitted from a substrate irradiated with ultraviolet light are utilized as a trigger for DC discharge, was investigated in this study; specifically, the DC discharge characteristics of PA-PECVD were examined for an Si substrate deposited in advance through hot-filament chemical vapor deposition with a nitrogen-doped diamond layer of thickness ∼1 μm. Using a commercially available Xe excimer lamp (hν = 7.2 eV) to illuminate the diamond surface with and without hydrogen termination, the photocurrents were found to be 3.17 × 1012 and 2.11 × 1011 electrons/cm2/s, respectively. The 15-fold increase in photocurrent was ascribed to negative electron affinity (NEA) caused by hydrogen termination on the diamond surfaces. The DC discharge characteristics revealed that a transition bias voltage from a Townsend-to-glow discharge was considerably decreased because of NEA (from 490 to 373 V for H2 gas and from 330 to 200 V for Ar gas), enabling a reduction in electric power consumption needed to synthesize diamond films through PA-PECVD. In fact, the authors have succeeded in growing high-quality diamond films of area 2.0 cm2 at 540 °C with a discharge power of only 1.8 W, plasma voltage of 156.4 V, and discharge current of 11.7 mA under the glow discharge of CH4/H2/Ar mixed gases. In addition to having only negligible amounts of graphite and amorphous carbon, the diamond films exhibit a relatively high diamond growth rate of 0.5 μm/h at temperatures as low as 540 °C, which is attributed to Ar+ ions impinging on the diamond surface, and causing the removal of hydrogen atoms from the surface through sputtering. This process leads to enhanced CHx radical adsorption, because the sample was applied with a negative potential to accelerate photoelectrons in PA-PECVD.