Doping is crucial to many potential applications of nanometer-sized semiconductors. Since their properties are strongly affected by both doping and quantum size effect, it is important to understand how dopants will influence its media under strong quantum confinement. In this dissertation, we will discuss the role of quantum confinement in the properties of nanometer-sized semiconductors doped with impurities. It is well-known that electronic and optical properties of nanometer-sized semiconductors can vary with size. We present size-dependent properties of lithium doped silicon and zinc oxide nanocrystals as examples. With the help of first-principles methods based on real space approach, we find that not only the size itself but also the chemical nature of the impurity is important to determine the properties of nanometer-sized semiconductors. We will also discuss size-induced magnetism in semiconductor nanostructures doped with non-magnetic impurities. From recent studies, it has been proposed that magnetic semiconductors can be designed by using non-magnetic defects, e.g., through the introduction of an extrinsic impurity atom that does not exhibit magnetism by itself. We examine this idea with silicon and zinc oxide nanostructures doped with impurities. We find that quantum size effect may induce magnetism in doped nanostructures. The evidence of the size-dependent magnetic properties offers a new perspective for the design of semiconductor-based spintronic materials.