This chapter reviews new research techniques and recent progress in the development and understanding of aluminium alloys by the application of advanced characterization for composition and structure determination. In particular, this chapter will focus on high-resolution transmission electron microscopy, atom probe tomography, and small-angle X-ray scattering, which all allow atomic-scale characterization. Furthermore, the complementary use of these techniques as well as correlation with other microscopy and microanalysis techniques, provide opportunities to overcome the inherent limitations of the individual methods and to capitalize on their unique advantages. This multitechnique approach will also be discussed in the context of both combinatorial studies and direct correlation with atomic-scale, first-principles modelling, namely density functional theory simulations, in the process of aluminium alloy development by investigating structure–property relationships.