Black arsenic (BAs) is a van der Waals layered material with a puckered honeycomb structure and has received increased interest due to its anisotropic properties and promising performance in devices. Here, crystalline structure, thickness-dependent dielectric responses, and ambient stability of BAs nanosheets are investigated using STEM imaging and spectroscopy. Atomic-resolution HAADF-STEM images directly visualize the three-dimensional structure and evaluates the degree of anisotropy. STEM-EELS is used to measure the dielectric response of BAs as a function of the number of layers. Finally, BAs degradation under different ambient environments is studied highlighting high sensitivity to moisture in the air.