The scanning electron microscope (SEM) is a powerful tool for analyzing the surface of various specimens. SEM observation at low voltage, which is typically lower than the 1 kV range, is very effective for obtaining surface information of specimens. However, at the low voltage range, resolution is restricted by the brightness and energy spread of electron sources. Therefore, to improve the resolution, a bright and monochromatic electron source is indispensable. In this work, we focused on an electron gun with a negative electron affinity photocathode using p-type GaAs and Cs–O adsorbates. The resolution of a prototype SEM was improved by approximately 16% compared with a SEM using a conventional Schottky emission (SE)-type emitter at the acceleration voltage of 1 kV. In addition, results showed that the measured brightness was as high as an SE-type emitter (∼107 A/m2/sr/V) and the estimated energy spread was less than 0.2 eV, which was narrower than that of a cold field emission-type emitter.