Wood presents a hierarchical structure, containing features at all length scales: from the tracheids or vessels that make up its cellular structure, through to the microfibrils within the cell walls, down to the molecular architecture of the cellulose, lignin, and hemicelluloses that comprise its chemical makeup. This structure renders it with high mechanical (e.g., modulus and strength) and interesting physical (e.g., optical) properties. A better understanding of this structure, and how it plays a role in governing mechanical and other physical parameters, will help to better exploit this sustainable resource. Here, recent developments on the use of advanced imaging techniques for studying the structural properties of wood in relation to its mechanical properties are explored. The focus is on synchrotron nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray tomographical imaging, Raman and infrared spectroscopies, confocal microscopy, electron microscopy, and atomic force microscopy. Critical discussion on the role of imaging techniques and how fields are developing rapidly to incorporate both spatial and temporal ranges of analysis is presented.