The electron spin polarization (ESP) at surfaces of bulk and artificially structured, thin film magnetic materials is studied using electron capture spectroscopy (ECS) and ion-induced emission of spin-polarized electron. For V and Tb surfaces, it is found that the temperature dependence of the surface magetic order is quite different from that of the bulk. For ultra-thin magnetic superlattices, V(100)/Ag(100) and Tb (0001)/W(110), we find novel magnetic surface anisotropies and critical behavior. At surfaces of 5 monolayers V(100) on Ag(100), the critical behavior of the surface-ESP is found to be identical to that of the two-dimensional Ising ferromagnet. At surfaces of PtMnSb and Fe80B20, we findnonzero ESP due to long-ranged or short-ranged ferromagnetic order. Thesign of the ESP at surfaces of the Heusler alloy PtMnSb is in agreement with recent band structure calculations. At surfaces of the spin glass Fe80B20, we find, in agreement with ECS data, that the ESP ofion-induced emitted spin-polarized electrons is extremely sensitive to the cleanness of thetopmost surface layer.