Grain boundary engineering (GBE) enhances the properties of metals by incorporating specific grain boundaries, such as twin boundaries (TB). However, applying conventional GBE to parts produced through additive manufacturing (AM) poses challenges, since it necessitates thermomechanical processing, which is not desirable for near-net-shape parts. This study explores an alternative GBE approach for post-processing bulk additively manufactured aluminium samples (KoBo extrusion), which allows thermo-mechanical treatment in a single operation. The present work was conducted to examine the microstructure evolution and grain boundary character in an additively manufactured AlSi10Mg alloy. Microstructural evolution and grain boundary character were investigated using Electron Back Scattered Diffraction (EBSD) and Transmission Electron Microscopy (TEM). The results show that along with grain refinement, the fraction of Coincidence Site Lattice boundaries was also increased in KoBo post-processed samples. The low-Σ twin boundaries were found to be the most common Coincidence Site Lattice boundaries. On the basis of EBSD analysis, it has been proven that the formation of CSL boundaries is directly related to a dynamic recrystallisation process. The findings show prospects for the possibility of engineering the special grain boundary networks in AM Al–Si alloys, via the KoBo extrusion method. Our results provide the groundwork for devising GBE strategies to produce novel high-performance aluminium alloys.