Future electron accelerators require DC high voltage photoguns to operate beyond the present state of the art to conduct new experiments that require ultra-bright electron beams with high average current and higher bunch charge. To meet these demands, the accelerators must demonstrate improvements in a number of photogun areas including vacuum, field emission elimination in high voltage electrodes, and photocathodes. This dissertation illustrates how these improvements can be achieved by the application of suitable thin-films to the photogun structure for producing ultra-bright electron beams.This work is composed of three complementary studies. First, the outgassing rates of three nominally identical 304L stainless steel vacuum chambers were studied to determine the effects of chamber coatings (silicon and titanium nitride) and heat treatments. For an uncoated stainless steel chamber, the diffusion limited outgassing was taken over by the recombination limited process as soon as a low outgassing rate of ~1.79(0.05) 10 -13 Torr L s -1 cm -2 was achieved. An amorphous silicon coating on the stainless steel chambers exhibited recombination limited behavior and any heat treatment became ineffective in reducing the outgassing rate. A TiN coated chamber yielded the smallest apparent outgassing rate of all the chambers: 6.44(0.05) 10 -13 Torr L s -1 cm -2 following an initial 90 °C bake and 2(20) 10 -16 Torr L s -1 cm -2 following the final bake in the series. This perceived low outgassing rate was attributed to the small pumping nature of TiN coating itself.Second, the high voltage performance of three TiN-coated aluminum electrodes, before and after gas conditioning with helium, were compared to that of bare aluminum electrodes and electrodes manufactured from titanium alloy (Ti-6Al-4V). This study suggests that aluminum electrodes, coated with TiN, could simplify the task of implementing photocathode cooling, which is required for future high current electron beam applications. The best performing TiNcoated aluminum electrode demonstrated less than 15 pA of field emission current at -175 kV for a 10 mm cathode/anode gap, which corresponds to a field strength of 22.5 MV/m. Third, the effect of antimony thickness on the performance of bialkali-antimonide photocathodes was studied. The high-capacity effusion source enabled us to successfully manufacture photocathodes having a maximum QE around 10% and extended low voltage 1/e lifetime (> 90 days) at 532 nm via the co-deposition method, with relatively thick layers of antimony (≥ 300 nm). We speculate that alkali co-deposition provides optimized stoichiometry for photocathodes manufactured using thick Sb layers, which could serve as a reservoir for the alkali.In summary, this research examined the effectiveness of thin films applied on photogun chamber components to achieve an extremely high vacuum, to eliminate high voltage induced field emission from electrodes, and to generate photocurrent with high quantum yield with an extended operational lifetime. Simult...