In the last couple of decades, high-performance electronic and optoelectronic devices based on semiconductor heterostructures have been required to obtain increasingly strict and well-defined performances, needing a detailed control, at the atomic level, of the structural composition of the buried interfaces. This goal has been achieved by an improvement of the epitaxial growth techniques and by the parallel use of increasingly sophisticated characterization techniques and of refined theoretical models based on ab initio approaches. This book deals with description of both characterization techniques and theoretical models needed to understand and predict the structural and electronic properties of semiconductor heterostructures and nanostructures.