Producing a brighter electron beams requires the smallest possible emittance from the cathode with the highest possible current. Several materials like ordered surface, single-crystalline metal surfaces, ordered surface, epitaxially grown high quantum efficiency alkali-antimonides, topologically non-trivial Dirac semimetals, and nano-structured confined emission photocathodes show promise of achieving ultra-low emittance with large currents. This work investigates the various limitations to obtain the smallest possible emittance from photocathodes, and demonstrates the performance of a novel electron gun that can utilize these photocathodes under optimal photoemission conditions. Chapter 2 discusses the combined effect of physical roughness and work function variation which contributes to the emittance. This is particularly seen in polycrystalline materials and is an explanation for their higher than expected emittance performance when operated at the photoemission threshold. A computation method is described for estimating the simultaneous contribution of both types of roughness on the mean transverse energy. This work motivates the need for implementing ordered surface, single-crystalline or epitaxially grown photocathodes. Chapter 3 investigates the effects of coulomb interactions on electron beams from theoretically low emittance, low total energy spread nanoscale photoemission sources specifically for electron microscopy applications. This computation work emphasizes the key role that image charge effects have on such cold, dense electron beams. Contrary to initial expectations, the primary limiter to beam brightness for theoretically ultra-low emittance photocathodes is the saturation current. Chapters 4 and 5 describe the development and commissioning of a high accelerating gradient, cryogenically cooled electron gun and photoemission diagnostics beamline within the Arizona State University Photoemission and Bright Beams research lab. This accelerator is unique in it's capability to utilize photocathodes mounted on holders typically used in commercial surface chemistry tools, has the necessary features and tools for operating in the optimal regime for many advanced photocathodes. A Pinhole Scan technique has been implemented on the beamline, and has shown a full 4-dimensional phase space measurement demonstrating the ability to measure beam brightness in this gun. This gun will allow for the demonstration of ultra-high brightness from next-generation ultra-low emittance photocathodes.