—Special misorientations between the bainite crystals in a high-carbon manganese–silicon steel, which were obtained during isothermal γ → α transformation at 300°C, have been studied using EBSD-based orientation microscopy. Sets of special boundaries have been compared with theoretical calculations of possible angles and axes of rotation of α crystals arising in the initial γ phase as a consequence of three types of orientation relationships: Kurdjumov–Sachs, Nishiyama–Wasserman, and intermediate. It has been shown that the special misorientations of α crystals taking into account the Brandon criterion correspond to Nishiyama–Wasserman and Kurdjumov–Sachs orientation relationships.