Al‐bearing medium‐Mn low‐density steels possess great potential in the automotive industry because of their excellent mechanical properties based on transformation‐induced plasticity and low specific weight. Reducing the austenite stability against deformation‐induced martensitic transformation enables a high strain‐hardening capacity to be obtained; however, undesirably low stability often results in considerably reduced tensile ductility and brittle fracture. Herein, the brittle fracture that occurs with increasing annealing temperature for a Fe−0.3C–9Mn−5Al (wt%) steel is investigated in relation to Mn segregation at the phase boundaries between ferrite and austenite. The results demonstrate that annealing at 850 and 900 °C leads to ductile fractures with 72% and 95% tensile elongation, respectively, whereas only 25% elongation is achieved for the specimen annealed at 950 °C, exhibiting predominant intergranular facets. 3D atom probe tomography reveals that annealing at 950 °C promotes considerable Mn segregation at the ferrite/austenite phase boundaries with a peak composition of ≈19 at%, which is sufficient to reduce the boundary cohesion for intergranular fracture. Thermodynamic moving boundary simulation reveals that intercritical annealing is not a prerequisite for segregations; however, low‐temperature and prolonged holding should be accompanied, such as the coiling procedures.