Catheter-based cardiovascular interventions (CBCVI) provide a fascinating context to study skill acquisition. In CBCVI, multiple cognitive skills are crucial; technical, perceptual, and decision-making skills are all used at the same time and often depend on each other. In order to be able to develop and implement the best possible medical education curriculum, it is important to understand cognition. Cognitive neuroscience studies the relationship between cognitive functions and brain processes. Recently, new techniques have become available that allow studying how learning changes specific brain structures and the connections between different brain areas. This chapter gives an overview of these studies. It also discusses the process of skill acquisition and the two types of knowledge on which learning is based on: declarative (know what) and procedural (know how) knowledge. Not only do these different types of knowledge have different representations and different properties. We discuss how changes in grey and white matter can be measured using different structural MRIs, and describe experimental studies on brain plasticity in declarative and procedural learning and skill acquisition.