<p>The effects of hot compression and subsequent annealing on the grain boundary character distribution (GBCD) were investigated in a 316L stainless steel. Not only low-level strain on the order of 0.1 but also relatively large strain such as 0.3 of hot deformation at 1100 °C and subsequent static recrystallization annealing could be used to enhance the fraction of Σ3ⁿ (<i>n</i> = 1, 2, 3…) type grain boundaries to more than 70 pct and hence to achieve grain boundary engineering. The release of stored energy as the result of dynamic recovery and dynamic recrystallization (DRX) has significant effects on the GBCD and grain size after the post-deformation static annealing. The sequential electron backscatter diffraction characterizations on a same region in between successive short annealing steps indicated that the formation of large size highly twinned grain-clusters is responsible for the high fractions of Σ3ⁿ boundaries. The grain-clusters could initiate from not only the nuclei of static recrystallization (SRX) but also from the DRX grains formed during hot deformation.</p>