Additive manufacturing, also known as three-dimensional printing, has provided a promising solution to produce near-net shape components directly from metallic powder. However, their surface roughness still prevents them from immediate use; finish machining is usually required. This study has investigated the grain size variation and saw-tooth/shear-band spacing during the machining of titanium alloy (Ti–6Al–4V) printed using direct metal deposition. Grain refinement was observed within both the printed and substrate regions, and their grain structures retained the basket-weave Widmanstätten and bimodal structures, respectively. The saw-tooth spacing decreased as the build height increased.