The connectivity between the boundaries is very important because the defect character of triple junctions is expected to have a significant influence on the bulk properties of materials, particularly mechanical behaviour. The investigation of triple junction investigations presented here indicates that a restricted Coincidence Site Lattice (CSL) model was found to be the most relevant and practicable for the characterisation of triple junctions in "Grain Boundary Engineered" materials. The triple junction character distribution was measured using the automated Electron Back-Scatter Diffraction (EBSD) application of Crystal Orientation Mapping (COM) for a series of thermomechanically processed copper and alpha-brass specimens. Triple junction character statistics were determined from COM data, automatically using a custom-built computer program, utilising the CSL model. The alpha-brass data were then compared with a series of previously acquired triple junction data for a series of strain-recrystallisation copper specimens. The main aim of the investigation was to determine the relationship between the grain boundary and triple junction character distributions, which was found to be essentially a linear relationship.