A new technique, Spin-Polarized Electron Emission Spectroscopy (SPEES), capable of investigating surface magnetism, has been successfully developed. SPEES allows us to energy- and spin-analyze electrons emitted during the interaction of a grazing-incidence ion beam with a solid surface. The energy and spin information obtained from the emitted electrons helps us to unravel the processes involved in ion-surface interactions at grazing angles. SPEES data obtained at Ni(110) picture-frame single crystals exhibit new characteristic features in the electron energy distribution that are strikingly different from that of electron-induced spectra. For the first time, two electron capture measurements, which are sensitive to "local" magnetic order existing on an atomic scale, have been performed at low energies (15-30 keV) at surfaces of the amorphous ferromagnet Fe\sb80B\sb20; the non-zero electron spin polarization amounts to 55%. These two new techniques open the way to study surface electronic and magnetic properties with unprecedented sensitivity.