AbstractIn multi‐component materials, triple phase boundary (TPB) is the location where reactions occur. A typical example is the TPB encountered in solid oxide fuel cells at the cathode–electrolyte interface. We proposed a tomographic approach that was developed based on serial sectioning using a focused dual ion beam (FIB) system. For image capture, FIB tomography was coupled with scanning electron microscopy, and differentiation of the composite cathode materials was possible through image contrast adjustment. An algorithm, built on the Hoshen–Kopelman theory, was then applied to measure TPB length. The percentage of the connected TPB line was also calculated with the algorithm for 3D computation. © 2011 Canadian Society for Chemical Engineering