Here we systematically investigate the crystallographic orientation relationship (OR) between MC-type precipitates (M, metal; C, carbon) and ferrite matrix in the Ti-Mo microalloyed steel with different processing. In the specimens without austenite deformation, the interphase precipitation can be obtained, and the precipitates obey Baker–Nutting (BN) OR with ferrite matrix. By contrast, in the specimens with austenite deformation, the supersaturated precipitates were formed in ferrite grains, which can obey BN, Nishiyama–Wasserman (NW), Kurdjumov–Sachs (KS) and Pitsch (P) ORs simultaneously. The cooling rate after austenite deformation can influence the OR between carbides and ferrite in the MC/ferrite system. At the cooling rate of 80 °C/s, carbides and ferrite can roughly satisfy these OR with the deviation ≥10°, while at the cooling rate of 20 °C/s, carbides and ferrite can strictly obey the specific OR. The energy accumulated in the deformation process and maintained in the fast-cooling process (80 °C/s) can offset the formation energy of the carbides. Thus, the carbides formed in the specimen with the cooling rate of 80 °C/s do not strictly satisfy the specific ORs to meet the rule of lowest energy, and then deviate by a small angle based on the specific ORs.