Sub-monolayers of titanium were deposited onto oxidised (100) single-crystal diamond surfaces and annealed in vacuo at temperatures up to 1000 °C to find a temperature-stable termination procedure that produces a surface with Negative Electron Affinity (NEA). The samples were analysed by X-ray Photoelectron Spectroscopy, Ultraviolet Photoelectron Spectroscopy and Energy-Filtered Photoemission Electron Microscopy to determine their electron affinity and work function values. NEA values were observed on samples following annealing above 400 °C, with the largest NEA value being –0.9 eV for a sample coated with a half-monolayer of Ti annealed at 400 °C. Work function values were ∼4.5 eV for all samples annealed at temperatures between 400 and 600 °C, then rose at higher temperatures due to the loss of substantial amounts of O from the surface. Work-function maps indicated that the surface was uniform over areas 5700 μm2, suggesting that the deposition and annealing steps used are reliable methods to produce films with homogeneous surface properties.