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We compare two quantities to describe a microstructure: the length fraction of Σ3/ Σ9‐grain boundaries and the number fraction of Σ3‐x‐x/ Σ3‐ Σ3‐ Σ9‐triple junctions using Cu, Ni and four of their alloys in several microstructural states. The fractions of Σ3‐grain boundaries show similar tendencies as the respective fractions of Σ3‐x‐x‐triple junctions in relation to the grain size upon deformation and annealing. However, the fraction of Σ9‐grain boundaries stagnates at certain grain sizes, while there is still a considerable change of Σ3‐ Σ3‐ Σ9‐triple junctions during grain growth, meaning that the Σ3‐ Σ3‐ Σ9‐triple junction microstructure is still evolving. To analyze the evolution of the triple junction microstructure, a program, such as pythorient, is necessary.