Thin films of black aluminum (B–Al) were prepared by pulsed DC magnetron sputtering in a mixture of argon + nitrogen (Ar + N2) gases with concentration of nitrogen 6%. At this concentration the process of anti-reflective surface (UV to near IR diffuse reflectance below 4%) formation is favored. The properties of such layers have been investigated using methods allowing to follow near-surface processes by means of thermally stimulated desorption (TSD) and thermally stimulated exo-electron emission (TSEE) in ultra-high vacuum conditions (p < 2.10−7 Pa). It is shown that at certain temperatures some adsorbed particles are desorbed and at the same time negative charges are emitted. In some cases, the emission sites are common. Comparison of TSEE measurements at three different excitations (α, proton irradiation and UV illumination) was performed. Common measurements together with calculations of the activation energies of desorption as well as electron emission sufficiently describe the centers responsible for these processes. In particular, the atomic oxygen Oat, the AlOH radical and partly the atomic nitrogen Nat together with the AlN radical are shown to play a significant role in this surface process.