A hybrid-structured ultrananocrystalline diamond (h-UNCD) film, synthesized on Si-substrates by a two-step microwave plasma enhanced chemical vapour deposition (MPECVD) process, contains duplex structure with large diamond aggregates evenly dispersed in a matrix of ultra-small grains (∼5 nm). The two-step plasma synthesized h-UNCD films exhibit superior electron field emission (EFE) properties than the one-step MPECVD deposited UNCD films. Nitrogen-ion implantation/post-annealing processes further improve the EFE properties of these films. Current imaging tunnelling spectroscopy in scanning tunnelling spectroscopy mode directly shows increased density of emission sites in N implanted/post-annealed h-UNCD films than as-prepared one. X-ray photoelectron spectroscopy measurements show increased sp2 phase content and C–N bonding fraction in N ion implanted/post-annealed films. Transmission electron microscopic analysis reveals that the N implantation/post-annealing processes induce the formation of defects in the diamond grains, which decreases the band gap and increases the density of states within the band gap of diamond. Moreover, the formation of nanographitic phase surrounding the small diamond grains enhanced the conductivity at the diamond grain boundaries. Both of the phenomena enhance the EFE properties.