As the fastest growing energy sector globally, shale and shale reservoirs have attracted the attention of both industry and scholars. However, the strong heterogeneity at different scales and the extremely fine-grained nature of shales makes macroscopic and microscopic characterisation highly challenging. Recent advances in imaging techniques have provided many novel characterisation opportunities of shale components and microstructures at multiple scales. Correlative imaging, where multiple techniques are combined, is playing an increasingly important role in the imaging and quantification of shale microstructures (for example, one can combine optical microscopy, SEM/TEM and X-ray radiography in 2D, or XCT and 3D-EM in 3D). Combined utilization of these techniques can characterize the heterogeneity of shale microstructures over a large range of scales, from macroscale to nanoscale (~10 0-10-9 m). Other chemical and physical measurements can be correlated to imaging techniques to provide complementary information for minerals, organic matter and pores. These imaging techniques and subsequent quantification methods are critically reviewed to provide an overview of the correlative imaging workflow. Applications of the above techniques for imaging particular features in different shales are demonstrated and key limitations and benefits summarized. Current challenges and future perspectives in shale imaging techniques and their applications are discussed.

Analyzing the development of fracture networks in shale is important to understand both hydrocarbon migration pathways within and from source rocks and the effectiveness of hydraulic stimulation upon shale reservoirs. Here we use time‐resolved synchrotron X‐ray tomography to quantify in four dimensions (3‐D plus time) the development of fractures during the accelerated maturation of an organic‐rich mudstone (the UK Kimmeridge Clay), with the aim of determining the nature and timing of crack initiation. Electron microscopy (EM, both scanning backscattered and energy dispersive) was used to correlatively characterize the microstructure of the sample preheating and postheating. The tomographic data were analyzed by using digital volume correlation (DVC) to measure the three‐dimensional displacements between subsequent time/heating steps allowing the strain fields surrounding each crack to be calculated, enabling crack opening modes to be determined. Quantification of the strain eigenvectors just before crack propagation suggests that the main mode driving crack initiation is the opening displacement perpendicular to the bedding, mode I. Further, detailed investigation of the DVC measured strain evolution revealed the complex interaction of the laminar clay matrix and the maximum principal strain on incipient crack nucleation. Full field DVC also allowed accurate calculation of the coefficients of thermal expansion (8 × 10−5/°C perpendicular and 6.2 × 10−5/°C parallel to the bedding plane). These results demonstrate how correlative imaging (using synchrotron tomography, DVC, and EM) can be used to elucidate the influence of shale microstructure on its anisotropic mechanical behavior.