Microstructural evolution of ultrananocrystalline diamond (UNCD) films in the bias-enhanced nucleation and growth (BEN-BEG) process in CH4/Ar plasma is systematically investigated. The BEN-BEG UNCD films possess higher growth rate and better electron field emission (EFE) and plasma illumination (PI) properties than those of the films grown without bias. Transmission electron microscopy investigation reveals that the diamond grains are formed at the beginning of growth for films grown by applying the bias voltage, whereas the amorphous carbon forms first and needs more than 30 min for the formation of diamond grains for the films grown without bias. Moreover, the application of bias voltage stimulates the formation of the nanographite phases in the grain boundaries of the UNCD films such that the electrons can be transported easily along the graphite phases to the emitting surface, resulting in superior EFE properties and thus leading to better PI behavior. Interestingly, the 10 min grown UNCD films under bias offer the lowest turn-on field of 4.2 V/μm with the highest EFE current density of 2.6 mA/cm2 at an applied field of 7.85 V/μm. Such superior EFE properties attained for 10 min bias grown UNCD films leads to better plasma illumination (PI) properties, i.e., they show the smallest threshold field of 3300 V/cm with largest PI current density of 2.10 mA/cm2 at an applied field of 5750 V/cm.