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.