We report on a new technique, spin-polarized electron emission spectroscopy. Using grazing-angle, surface scattering of H +and He+ ions at Ni(llO), we find that the angle-resolved energy distribution of emitted spin-polarized electrons is significantly different from that of electron-induced secondary (cascade) electrons and exhibits a series of characteristic "peaks" (including element-specific Auger electrons). We obtain characteristic, spin-dependent information on the surface electronic structure of NiOIO) and on atom-surface charge-transfer processes. PACS numbers: 79.20.Rf, 61.14.Rq, 75.20.En Recently, broad and intense scientific interest has focused on the two-dimensional (20) physical properties of surfaces of thin films and bulk materials. 1 • 2 Grazing-ion surface reflection is a powerful means to probe these properties, in particular, the electronic, magnetic, and even chemical properties of surfaces. At grazing angles of incidence, ions do not penetrate a flat surface, they are specularly reflected and, therefore, probe the topmost surface layer. This is profitably exploited in electroncapture spectroscopy (ECS), 3 • 4 where capture of spinpolarized electrons by grazing-angle surface reflected deuterons is used to obtain information on surface magnetic behavior such as long-and short-ranged magnetic order, critical behavior, and 20 phase transitions. 5 In recent years, a series of further spin-sensitive techniques has been devised and most successfully applied to study surface magnetism, 2 • 6 but none of them fulfills all the requirements of simultaneously being extremely surface, spin, and element specific.In this Letter, we report on a new and powerful method, energy-and angle-resolved, spin-polarized electron emission spectroscopy (SPEES), where grazingangle ion-surface reflection is used to induce the emission of spin-polarized electrons from the topmost layer of magnetic surfaces. Specifically the capability to detect element-specific, spin-polarized Auger electrons makes SPEES a very unique spectroscopy. Two other techniques are remotely related to SPEES: Electroninduced, spin-polarized Auger-electron spectroscopy (SPAES) successfully developed by Landolt, Allenspach, and Mauri 7 and ion neutralization spectroscopy 8 (INS) pioneered by Hagstrum and used to probe local electron density of states outside the surface.An important aspect of SPEES is that it not only allows us to study the electronic, magnetic, and chemical structure of surfaces, but also enables us to unravel the physics of electronic charge-exchange processes occurring during particle surface interaction, which, at present, receives a great deal of attention. 9 -11 We employ the "spin" of emitted electrons as an additional "label" to identify various processes occurring in ion-surface interaction at grazing incidence. Selecting, for the incoming ions, grazing angles of incidence significantly helps to avoid cascade effects caused by energetic secondary electrons or ions and reveals important details about these processes.I...