Wide bandgap semiconductors such as diamond and the III–V nitrides (GaN, AlN, and AlGaN alloys) exhibit small or even negative electron affinities. Results have shown that different surface treatments will modify the electron affinity of diamond to cause a positive or negative electron affinity (NEA). This study describes the characterization of these surfaces with photo-electron emission microscopy (PEEM). The PEEM technique is unique in that it combines aspects of UV photoemission and field emission. In this study, PEEM images are obtained with either a traditional Hg lamp or with tunable UV excitation from a free electron laser. The UV-free electron laser at Duke University provides tunable emission from 3.5 to greater than 7 eV. PEEM images of boron or nitrogen (N)-doped diamond are similar to SEM of the same surface indicating relatively uniform emission. For the N-doped samples, PEEM images were obtained for different photon energies ranging from 5.0 to 6.0 eV. In these experiments, the hydrogen terminated surface showed more intense PEEM images at lower photon energy indicating a lower photothreshold than annealed surfaces which are presumed to be adsorbate free. For the nitrides, the emission properties of an array of GaN emitter structures is imaged. Emission is observed from the peaks, and relatively uniform emission is observed from the array. The field at the sample surface is approximately 10 V/μm which is sufficient to obtain an image without UV light. This process is termed field emission electron microscopy (FEEM).